Improvements in the Manufacture of Artificial Musk.
Year: 1891

page_text: Date of Application, 12th Aug., 1891
Complete Specification Left, 20th Apr., 1892-Accepted, 25th June, 1892
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of Artificial Musk.
I, ALBERT BAUR, of Mulhouse, Alsace, Doctor, do hereby declare the nature
of this invention to be as follows:-
to me.
A Patent No. 4963 of 1889 for the manufacture of artificial musk was granted
The process consisted in treating by a mixture of nitric and sulphuric
acids the hydrocarbon, boiling from 1700 to 200°, obtained by the reaction of
chloride (bromide or iodide) of isobutyle on toluene in the presence of chloride of
aluminium. The nitro derivative thus prepared formed yellowish white crystals,
having a strong smell of musk.
The scientific investigation of this reaction, to which I have long been devoting
my attention, has proved that the hydrocarbon boiling from 170° to 200° was a
mixture of a great many constituents, the principal one being butyltoluene, the
others butylbenzene, butylxylene, butylethylbenzene, and the corresponding
amylic compounds, and finally, but in a smaller proportion, the corresponding
propylic derivatives.
The xylene and ethylbenzene derivatives owe their formation to the xylene and
ethylbenzene always contained in the toluene of commerce; on the other hand,
they are formed also by the toluene itself, this substance being transformed
partially by the action of chloride of aluminium into benzene, xylene, ethylbenzene
and other hydrocarbons (vide Friedel and Crafts: "Comptes rendus de l'Academie
des Sciences de Paris"-vol. 101 p. 1218). The propylic and amylic compounds
are derived from the corresponding alcohols, always contained in butylic alcohol of
commerce.
I have prepared in a state of purity all these bodies, and I have found that, by
treatment with nitric and sulphuric acids, they yield all musk-smelling nitro
derivatives.
The latter differ in their properties very little, and in uo essential point, from the
nitro-derivative of butyltoluene, the trinitrobutyltoluene, especially the odour of
the propylic derivative, is a very weak one.
The huteltoluene is the tertiary compound
[Price 8d.]
(CH
CH{CnHọn+1
(NO)
(or C₂H, or C,H)

page_text: are no longer simple homologues of those for which I have obtained a Patent, and
I therefore apply for a new Patent to protect the same.
Betylanisol C H
✓OCH,
\CH,
when nitrated,.gives a substance in which the smell
of musk is hardly perceptible, and the nitro derivatives of the butylated para- and
ortho cresolethers do not offer any remarkable property.
But the nitro-derivatives of the butylated, amylated and propylated meta cresol-
ethers, and in general of the meta substitute phenol-ethers, smell like musk, and I
shall describe their preparation as follows.
I mix, for instance, 100 parts of the methylic ether of meta cresol with 50 parts
of chloride of iso or pseudo butyle and 6 parts of chloride of aluminium, and I
heat on the water bath, until no more hydrochloric acid is evolved, i.e. about
24 hours.
Instead of chloride of aluminium, chloride of iron or another equivalent may be.
used.
The product of the reaction is poured into water and distilled with steam, and
the butylated cresol ether is isolated by fractioned distillation.
It forms an
aromatically smelling colourless liquid, boiling at 2220-224°.
If instead of pure butylic chloride, the derivative of commercial butylic alcohol
is used, I obtain a mixture of butylic, propylic and amylic ethers, boiling between
200° and 240°.
In order to obtain the musk substitute the ether is introduced gradually into a
large quantity of fuming nitric acid, or into a mixture of nitric and sulphuric acids,
and the mixture is heated in a water bath until a sample poured into water solidifies.
The whole product is then poured into water or on to ice, filtered, washed to
eliminate the acid and recrystallized from alcohol or another solvent. By this way
I obtain yellowish white needles, possessing a strong musky odour.
Instead of butylic chloride, amylic or propylic chlorides may be used in the,
preparation of the substituted phenol ether.
It is also possible to obtain the result by acting on other phenolethers with
amylene, butylene, or propylene in presence of chloride of aluminium. The
OCH,
propyl cresol ether C¸H‚—CH,: boils from 100° to 200°, the amylic derivative

page_text: I can, finally, also prepare substances of the above mentioned composition by
introducing first the butylic, propylic or amylic radicles into meta cresol, nitrating
the butyl (amyl or propyl) cresol thus obtained by means of nitric or nitric and
sulphuric acids and transforming the nitro-derivatives into their ethers by the usual
methods. Or I may prepare first the ethers of the above mentioned butylated &c.
metacresol and nitrate the same afterwards.
Dated this 10th day of troust 1901
ABEL & IMRAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Improvements in the Manufacture of Artificial Musk.
I, ALBERT BAUR, of Mulhouse, Alsace Doctor 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:-
to me.
A Patent No. 4963 of 1889 for the manufacture of artificial musk was granted
The process consisted in treating by a mixture of nitric and sulphuric acids
the hydrocarbon, boiling from 170° to 200°, obtained by the reaction of chloride
(bromide or iodide) of isobutyle on toluene in the presence of chloride of
aluminium. The nitro derivative thus prepared formed yellowish white crystals,
having a strong smell of musk.
The scientific investigation of this reaction, to which I have long been devoting
my attention, has proved that the hydrocarbon boiling from 170° to 200° was a
mixture of a great many constituents, the principal one being butyltoluene, the
others butylbenzene, butylxylene, butylethylbenzene, and the corresponding amylic
compounds, and finally, but in a smaller proportion, the corresponding propylic
derivatives.
The xylene and ethylbenzene derivatives owe their formation to the xylene and
ethylbenzene always contained in the toluene of commerce; on the other hand,
they are formed also by the toluene itself, this substance being transformed partially
by the action of chloride of aluminium into benzene, xylene, ethylbenzene and
other hydrocarbons (vide Friedel and Crafts: "Comptes rendus de l'Academie
des Sciences de Paris"-vol. 101 p. 1218). The propylic and amylic compounds
are derived from the corresponding alcohols, always contained in butylic alcohol of
commerce.
I have prepared in a state of purity all these bodies, and I have found that, by
treatment with nitric and sulphuric acids they all yield musk-smelling nitro
derivatives. The latter differ in their properties very little, and in no essential
point, from the nitro derivative of butyltoluene, the trinitrobutyltoluene, especially
the odour of the propylic derivative, is a very weak one.
The butyltoluene is the tertiary compound

page_text: It seems that all the trinitro derivatives of the aromatic hydrocarbons of the
general formula
are no longer simple homologues of those for which I have obtained a Patent, and
I therefore apply for a new Patent to protect the same.
Butylanisol CH
✓ OCH 3
CH
when nitrated, gives a substance in which the smell
of musk is hardly perceptible, and the nitro derivatives of the butylated para- and
ortho cresol ethers do not offer any remarkable property.
But the nitro derivatives of the butylated, amylated and propylated metacresol-
ethers, and in general of the meta substitute phenol-ethers, smell like musk, and I
shall describe their preparation as follows:
I mix, for instance, 100 parts of the methylic ether of meta cresol with 50 parts
of chloride of iso or pseudobutyle and 6 parts of chloride of aluminium, and I heat
on the water bath, until no more hydrochloric acid is evolved, i.e. about 24 hours.
Instead of chloride of aluminium, chloride of iron or another equivalent substance
may be used.
The product of the reaction is poured into water and distilled with steam, and
the butylated cresol ether is isolated by fractioned distillation. It forms an
aromatically smelling colourless liquid, boiling at 222°-224°.
If instead of pure butylic chloride, the derivative of commercial butylic alcohol
is used, I obtain a mixture of butylic, propylic and amylic ethers, boiling between
200° and 240°.
In order to obtain the musk substitute the ether is introduced gradually into a
large quantity of fumming nitric acid, or into a mixture of nitric and sulphuric acids,
and the mixture is heated in a water bath until a sample poured into water solidifies.
The whole product is then poured into water or on to ice, filtered, washed to
eliminate the acid and recrystallized from alcohol or another solvent. By this way
I obtain yellowish white needles, possessing a strong musky odour.
Instead of butylic chloride, amylic or propylic chlorides may be used in the
preparation of the substituted phenol ether.
It is also possible to obtain the result by acting on other phenolethers with
amylene, butylene or propylene in presence of chloride of aluminium. The
OCH,
propyl cresolether C,H,C,H, boils from 100° to 200°, the amylic derivative

page_text: The nitration is the same as above described.
1 can, finally, also prepare substances of the above mentioned composition by
introducing first the butylic, propylic or amylic radicles into meta-cresol, nitrating
the butyl (amyl or propyl) cresol thus obtained by means of nitric or nitric and
sulphuric acids and transforming the nitro-derivatives into their ethers by the usual
methods. Or I may prepare first the ethers of the above mentioned butylated &c.
metacresol and nitrate the same afterwards.
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 for preparing the nitro derivatives of the
butylated, propylated or amylated ethers of metacresol, or other substituted
phenols.
2. The artificial musk being a trinitroderivative of the butylated, amylated or
propylated metacresol ethers or other meta substituted phenol ethers produced in a
white crystalline form, substantially as herein described.
Dated this 20th dow of A il 1000
ABEL & IMRAY,
Agents for the Applicant.