Improvements in the Process of Making Artificial Musk.
Year: 1896

page_text: Date of Application, 5th May, 1896-Accepted, 6th June, 1896
COMPLETE SPECIFICATION.
[Communicated from abroad by Messrs. GRETSCH AND MAYER, of 96 and 98 Fulton
Street, in the City, County, and State of New York, United States of
America, Merchants.]
Improvements in the Process of Making Artificial Musk.
I SAMUEL SIDNEY BROMHEAD 97 Newgate Street, London, Patent Agent,
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 :-
This invention relates to the manufacture of artificial musk, and its novel
features consist in the specific method of treating hydrocarbons of the aliphatic
series with sulphuric and nitric acid and in the method of purifying the product.
It is well known, that long ago, substances or mixtures of substances of musk-like
odor have been obtained by the action of sulphuric and nitric acid on naphtha,
kerosene or certain hydrocarbons, contained in the crude petroleum.
Warren de la Rue in. 1856, and Bussenius and Eisenstamm in 1860 described a
process by which they obtained compounds or solutions of musk-like odor from
kerosene, but for several obvious reasons their processes never could be used in
practice.
By the action of sulphuric acid upon kerosene or certain hydrocarbons contained
therein, sulfo acids of unknown composition are formed which are soluble in water.
By the action of nitric acid upon these products, they are transformed into
crystallized nitro products bearing, after Bussenius and Eisenstamm the
formulas C'H'(NO) and CH(NO) and described as di- and trinitropetroles.
Simultaneously with these compounds an oily substance of a very intense musk-
like odor is formed which seems likewise to be a nitroproduct and which by the aid
of sulphuretted ammonia is reduced to an amido compound.
But even this product has no value as perfume, as its odor is disagreeable and
as far as I am aware, no method of its purification has been found up to the present
time.
My method consists in the saturation of ice cold sulphuric acid with the soluble
parts of kerosene or naphtha, containing mainly the hydrocarbons octane, nonane
and decane and treating the saturated sulphuric acid with one fourth of its voluine
of nitric acid of a specific gravity of 200 Beaumé. The nitric acid is stirred in
slowly.
To obtain a complete saturation of the ice cold sulphuric acid with the soluble
parts of the kerosene or naphtha I proceed as follows:
I take for instance one pound of sulphuric acid and shake it thoroughly in a
separatory funnel with its volume of naphtha, and by means of their difference in
specific gravity, the two fluids will separate quickly. I then draw off the sulphuric
acid, which I use again to become saturated with another quantity of naphtha, and
repeat this process until the sulphuric acid turns intensely dark and will not become
further saturated with the soluble naphthene-carbonic acids contained in the
naphtha, which acids form the base from which I prepare the artificial musk.
The saturated solution thus obtained is then nitrated in the manner above
described.
The nitrated product is slowly heated up to from 100 to 150 degrees Celsius and
poured into at least ten times its volume of ice cold water. The mixture is then
neutralized with ammonia or any other alkali and mixed with a neutral soap

page_text: prepared from rosin, the quantity of rosin being approximately equal to the
quantity of sulphuric acid originally used. The solution is then precipitated with
a solution of a metal salt, for instance sulphate of aluminium, magnesium, calcium,
strontium or the like, and the precipitate filtered and carefully washed with water.
It contains all the musk-smelling substances in a very pure state. If for instance
alumina is used for precipitating, the precipitate can be washed with alcohol and
the alcoholic solution contains the purified musk.
If magnesia is used the precipitate forms a white powder with a very strong
musk-like odor, which for many purposes may be used directly.
Instead of rosin, I may use oleic-, or stearic acid as soap solution, but for many
reasons I prefer to use rosin or abietic acid.
Having now particularly described and ascertained the nature of my said
invention, and in what manner the same is to be performed, I declare that what
I claim is :-
1. In a method of preparing artificial musk, the production of the base for the
musk by the saturation of sulphuric acid at a low temperature with the soluble
naphthene-carbonic acids contained in naphtha or kerosene, and the subsequent
nitration of the solution, substantially as and for the purposes hereinbefore
described.
2. In a method of preparing artificial musk, first saturating sulphuric acid at a
low temperature with the soluble naphthene-carbonic acids contained in naphtha or
kerosene; secondly, nitrating the solution thus formed, and then gradually heating
the product, substantially as and for the purposes described.
3. The method of preparing artificial musk which consists: first, in treating
kerosene or naphtha with sulphuric and nitric acid, second, neutralizing the
product of reaction with an alkali and third, precipitating the odoriferous substance
with a metallic soap, substantially as and for the purposes herein before described
and set forth.
4. The method of preparing artificial musk which consists first: in saturating
sulphuric acid with the soluble parts of kerosene or naphtha at a low temperature,
second, nitrating this saturated solution, third, gradually heating the nitrated
product to a suitable temperature, fourth, neutralizing the nitrated product with
an alkali, fifth, precipitating the neutralized product by means of a metallic soap,
substantially as and for the purposes hereinbefore described and set forth.
Dated this 5th day of May 1896.
S. S. BROMHEAD.