Improvements in the Manufacture of Artificial Musk.
Year: 1895

page_text: Date of Application, 21st Aug., 1895
Complete Specification Left, 1st May, 1896-Accepted, 25th July. 1896
[Communicated from abroad by THE FABRIQUES De Produits Chimiques de
THANN ET DE MULHOUSE, of Thann, Alsace.]
Improvements in the Manufacture of Artificial Musk.
I, CHARLES DENTON ABEL, of No. 28 Southampton Buildings, Chancery
Lane, in the County of London, Consulting Engineer and Chartered Patent Agent
do hereby declare the nature of this invention to be as follows:-
The artificial musks hitherto known are the trinitroderivatives and are all
derivatives of butylated (or propylated or amylated) aromatic hydrocarbons,
containing three nitro-groups or two nitro and one cyanogen-group, for instance
trinitrobutylxylene, C. (CH), (CH) (NO2), or dinitrocyanobutylxylene C, (CH,),
(CH) (NO), (CN).
My foreign correspondents have now discovered that one of the three nitro-
groups of the trinitrobutylxylene may be substituted not only by a cyanogen-group'
but also by a haloid atom, for instance, Cl Br or I.
In order to prepare these dinitro-haloid-butylxylenes two different methods may
be used.
1st. One atom of halogen (CI Br I) is introduced in butylxylene and the haloid
derivative thus obtained is treated with nitric acid.
2nd. Trinitrobutylxylene is transformed by reduction into dinitroamidobutylxylene:
C. (CH), (CH) (NO,), (NH2), and the amido-group in this latter replaced
by a halogen in the usual way, by diazotising and treating afterwards with cuprous
chloride or bromide or with hydriodic acid.
My correspondents have prepared by either of these methods:
1. The bromodinitrobutylxylene :
long white needles or prisms, melting point 73° C., insoluble in water, soluble in
alcohol, ether and other usual organic solvents.
2. The iododinitrobutylxylene, yellowish needles, soluble in alcohol and ether,
melting point 105° C.
3. The chlorodinitrobutylxylene, needles, melting point 82° C., also soluble in
alcohol and ether.
By way of example the description of the preparation of the first of the bodies
according to the two methods is given.
1.-1 kilo. of bromine is poured gently into 1 kilo. of butylxylene, mixed with
a small quantity of iodine and kept thoroughly cool, and the mixture is allowed to
stand for some time. When it is solidified it is put into water, washed with
dilute sulphurous acid, with alkali and finally with water, and crystallised out of
alcohol.
The monobromobutvlxylene

page_text: The brominated, hydrocarbon is now, put into 10 parts of fuming nitric
acid (98-100%) or into a mixture of nitric and sulphuric acids. After a few
hours, the mixture is poured into water, well washed and crystallised several times
out of alcohol.
The body thus obtained is according to the elementary analysis a bromodinitro-
butylxylene, C (CH3)2 (CH) Br (NO2)2. It crystallises in fine white needles
or prisms, melting point 73° C., is insoluble in water, soluble in alcohol, ether, etc.
and possesses a strong musk like odour.
11. In the second method for obtaining the bromodinitrobutylxylene, dinitro-
butylxylidine C (CH), (CH) (NO2)2 (NH2) must first be prepared.
For this purpose 1 kilo. of trinitrobutylxylene is put into 10 kilos. of alcohol, a
solution of sulph-bydrate of ammonia, containing one and a half or two times the
theoretical amount (viz. 150-200 gr. of H2S) is added and the mixture heated on
the water bath until the colour of the solution is light yellow.
The reduction takes place according to the equation:
When the reduction is finished, the greater part of the alcohol is distilled off
and the residue poured into water, the dinitrobutylxylidine is precipitated, filtered
and crystallised in alcohol. It forms yellow needles or prisms, insoluble in water,
soluble in alcohol, ether and other organic solvents, melting point 170° C.
The dinitrobutylxylidine is afterwards diazotised in solution in strong hydro-
chloric or sulphuric acid and the diazo-compounds poured into a solution of cuprous
bromide in hydrobromic acid.
The solution is heated until no more uitrogen evolves.
The reaction takes place according to the equation :
The bromodinitrobutylxylene which precipitates, is purified by crystallisation
from alcohol. It is identical with that one which is obtained by nitration of
bromobutylxylene.
In an analogous manner the corresponding chloro- and iodo derivatives may be
obtained.
ABEL & IMRAY,
Agents for the Applicant.
Improvements in the Manufacture of Artificial Musk.
1, CHARLES DENTON ABEL, of No. 28 Southampton Buildings, Chancery Lane,
in the County of London, Consulting Engineer and Chartered 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 :-
The artificial musks hitherto known are the trinitroderivatives and are all
derivatives of butylated or propylated or amylated aromatic hydrocarbons,
containing three nitro-groups or two nitro and one cyanogen-group, for instance

page_text: trinitrobutylxylene, C. (CH₂), (CH) (NO,), or dinitrocyanobutylxylene C. (CH₂),
(CH) (NO), (CN).
My foreign correspondents have now discovered that for one of the three nitro-
groups of the trinitrobutylxylene may be substituted not only a cyanogen-group
but also a haloid atom, for instance, CI, Br or I.
In order to prepare these dinitro-haloid-butylxylenes, two different methods may
be used.
1st. One atom of halogen (Cl, Br or I) is introduced into butylxylene, and the
haloid derivative thus obtained is treated with nitric acid, or
2nd. Trinitrobutylxylene is transformed by reduction into dinitroamidobutylxylene,
C.(CH), (C.H.) (NO), (NH,) and for the amido-group in this latter is substituted
a halogen in the usual way, by diazotising and treating afterwards with cuprous
chloride or bromide or with hydriodic acid.
My correspondents have prepared by either of these methods-
1 The hromadinitrabutyly vlong
thus obtained crystallises in thin white needles, melting point 45° C.
The brominated hydrocarbon is now put into 10 parts of fuming nitric acid, of
98 to 100 per cent., or into a mixture of nitric and sulphuric acids. After a few
hours, the mixture is poured into water, well washed and crystallised several times
out of alcohol.
The body thus obtained is according to the elementary analysis a bromodinitro-
butylxylene, C. (CH,), (C.H.) Br (NO,),. It crystallises in fine white needles or
prisms, melting point 73° C., is insoluble in water, soluble in alcohol, ether, etc.,
and possesses a strong musk like odour.
II. In the second method for obtaining the bromodinitrobutylxylene, dinitro-
butylxylidine C, (CH), (CH) (NO,), (NH,) must first be prepared.
For this purpose, 1 kilo. of trinitrobutylxylene is put into 10 kilos. of alcohol, a
solution of sulph-hydrate of ammonia, containing one and a half or two times the
theoretical amount (viz. 150 to 200 gr. of H,S) is added and the mixture is heated
on the water bath until the colour of the solution is light yellow.
The reduction takes place according to the equation:

page_text: and the residue poured into water; the dinitrobutylxylidine is precipitated, filtered;
and crystallised in alcohol. It forms yellow needles or prisms, insoluble in water,.
soluble in alcohol, ether and other organic solvents, melting point 170° C.
The dinitrobutylxylidine is afterwards diazotised in solution in strong hydro-.
chloric or sulphuric acid, and the diazo-compounds poured into a solution of cuprous
bromide in hydrobromic acid.
The solution is heated until no more nitrogen is evolved.
The reaction takes place according to the equation:
The bromodinitrobutylxylene which precipitates, is purified by crystallisation
from alcohol. It is identical with the product obtained by nitration of bromo-
butylxylene.
In an analogous manner the corresponding chloro- and iodo-derivatives may be
obtained.
Having now particularly described and ascertained the nature of this 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 halogenodinitroderivatives of
butylxylene,
a.) by nitration of halogenated butyl-xylenes.
b.) by substitution for the HN-group, in dinitroamidobutylxylene C. (CH,),
(CH) (NO), (NH) a halogen-group, according to the well known
methods (diazotation and treatment with a halogenhydric with or without
the presence of the corresponding cuprous salt).
2. The halogenodinitroderivatives of butylxylene prepared as above set forth.
Dated this 1st day of May 1896.
ABEL & IMRAY,
Agents for the Applicant.