Process for the Manufacture of Substitutes for Natural Musk.
Year: 1896

page_text: Date of Application, 6th Oct., 1896-Accepted, 2nd Jan., 1897
COMPLETE SPECIFICATION.
Process for the Manufacture of Substitutes for Natural Musk.
I, MAURICE DINESMAN, of 5, Passage Gourdon, Paris, France, Engineer and
Chemist 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, that is to say :-
My invention has for its object the commercial mauufacture of products capable
of substitution for natural musk in perfumery.
In carrying out my process, I employ the following as the raw materials: All
the isomeric-butyl-toluidines, having the formula C.H, (CH) (CH) (NH),
such as 3-iso-butyl-ortho-toluidine, 5-pseudo-butyl-ortho-toluidine, &c., and their
homologues, such as butyl-xylidine, ethyl-butyl-toluidine, amyl-toluidine, amyl-
xylidine, &c.
My said process consists of the two following principal operations:
1. The conversion of the raw materials, above mentioned, into their corre-
sponding mono-nitro-hydrocarbons, and
2. The nitration of the mono-nitro-hydro-carbons thus obtained.
To render my invention readily understood, I will describe the same in detail,
together with the means for carrying out the two phases of the process.
I. THE CONVERSION OF THE 3 ISO-BUTYL-ORTHO-TOLUIDINE, OF THE 5 PSEUDO
BUTYL-ORTHO-TOLUIDINE, AND OF THEIR ISOMERS AND HOMOLOGUES,
INTO MONO-NITRO-ISO-BUTYL TOLUENE, INTO MONO-NITRO PSEUDO-BUTYL-
TOLUENE, AND INTO THEIR ISOMERS AND HOMOLOGUES.
Example A.-Into a mixture of 2 molecules of nitric acid and ice, I introduce
1 molecule of 3-iso-butyl-ortho-toluidine, the quantity of ice being about three
times the weight of the iso-butyl-ortho-toluidine. There is precipitated the
nitrate of iso-butyl-toluidine. I then add, little by little, 2 molecules of nitrite of
sodium, carefully cooling it at the same time. The nitrate of iso-butyl-toluidine
dissolves out almost completely, and nitrate of di-azo-iso-butyl-toluene is formed.
This cold solution is then poured into a large vessel containing a preparation of
protoxide of copper, or other oxides of metals, such as iron, or silver, or these
metals themselves in very fine powder. This preparation of the protoxide of
copper is obtained by quickly pouring a corresponding quantity of caustic soda
into a boiling solution composed of a mixture of sulphate of copper and glucose,
and quickly cooling it. Each drop of the solution of the diazo-iso-butyl-toluene
poured into the fresh and cold preparation containing the protoxide of copper,
produces a strong disengagement of nitrogen, and gives rise to nitro-iso-butyl-
toluene which is possessed of an agreeable odour. When the whole of the solution
of the diazo-iso-butyl-toluene has been poured out, it is allowed to stand for some
hours. The mono-nitro-iso-butyl-toluene is removed by a strong current of steam
and is then extracted by ether, cooled, and, if necessary, rectified in vacuo.
Example B. At a low temperature, I nitrate 1 part of 5-pseudo-butyl-ortho-
toluidine dissolved in 9 parts of sulphuric acid, with a little more than 1 molecule
of nitric acid dissolved in 5 parts of sulphuric acid. I then pour it on to ice
(sufficient to prevent undue heating) and saturate it with carbonate of soda until a
feeble acid reaction is obtained. The mono-nitro-psendo-butyl-ortho-toluidine

page_text: (mixed with more strongly nitrated products) is then precipitated. I now wash it
and separate out the liquid by filtration. I next add to 1 part of this mono-nitro-
pseudo-butyl-toluidine 3 parts of alcohol and 1 part of sulphuric acid, together
with a little more than 1 molecule of nitrite of sodium (or nitrous acid). I carefully
heat it until complete disengagement of the nitrogen takes place, and I then heat
it in a bain-marie to evaporate the alcohol and volatile products obtained in the
reaction. A mixture of the isomeric mono-nitro-pseudo-butyl-toluenes now remains
which possesses an agreeable odour. It is then purified by distillation with steam
and rectified in vacuo.
(mixed with more strongly nitrated products) is then precipitated. I now wash it
and separate out the liquid by filtration. I next add to 1 part of this mono-nitro-
pseudo-butyl-toluidine 3 parts of alcohol and 1 part of sulphuric acid, together
with a little more than 1 molecule of nitrite of sodium (or nitrous acid). I carefully
heat it until complete disengagement of the nitrogen takes place, and I then heat
it in a bain-marie to evaporate the alcohol and volatile products obtained in the
reaction. A mixture of the isomeric mono-nitro-pseudo-butyl-toluenes now remains
which possesses an agreeable odour. It is then purified by distillation with steam
and rectified in vacuo.
11. NITRATION OF THE MONO-NITRO-ISO-BUTYL TOLUENE AND MONO-NITRO-
PSEUDO-BUTYL-TOLUENE ABOVE OBTAINED, AND THEIR ISOMERS AND
HOMOLOGUES TO OBTAIN MUSK.
For this purpose, I treat 1 part of the mono-nitro-iso-butyl-toluene, or 1 part of
the mono-nitro-pseudo-butyl-toluene, with a mixture of 4 parts of fuming nitric
acid and 8 parts of fuming sulphuric acid, taking care to cool it by cold water in
order to calm the reaction which, from the commencement, is very violent. I then
heat it in a bain-marie for 9 hours, decant it, and add again an equal quantity of
the mixture of the same acids. I re-heat it for 12 hours, in the bain-marie, allow
it to cool, and pour it on to ice. Tri-nitro-iso-butyl-toluene, or tri-nitro-pseudo-
butyl toluene separates out, which is, at first oily, but soon crystallises. I then
wash out by means of diluted caustic soda and crystallise in alcohol. The crystals
thus obtained smell strongly of musk, and may advantageously be used in
perfumery, as a substitute for natural musk.
Having now particularly described, and ascertained the nature of my said inven-
tion, and in what manner the same is to be performed, I declare that what I
claim is :
1. The herein described process which cousists 1st, in converting into corre-
sponding mono-nitro-hydro-carbons all the isomeric butyl toluidines, such as the
3-iso-butyl-ortho-toluidine, 5 pseudo-butyl-ortho-toluidine, and its isomers and
homologues, such as butyl-xylidine &c., either by diazotising and treating them
with protoxide of copper, or by treating them with a mixture of sulphuric acid
and nitric acid, separating the nitrated bases thus obtained, and converting them,
by nitrous acid and alcohol, into their corresponding mono-nitro-hydrocarbons:
and 2nd, in treating the mono-nitro-hydrocarbons, obtained in the first operation,
with a mixture of fuming nitric and sulphuric acids, in order to obtain the musk.
2. My improved process for the manufacture of substitutes, suitable for use in
perfumery, for natural musk, substantially as described.
Dated this 6th day of October 1806
ERNEST DE PASS,
Chartered Patent Agent,
78, Fleet Street, London, and 54, Market Street, Nottingham,
Agent for the Applicant.