Year: 1897

page_text: I, OLIVER IMRAY, of Birkbeck Bank Chambers, Southampton Buildings, Chancery
Lane, in the County of London, Chartered Patent Agent, do hereby declare tho
nature of this invention (as communicated to me from abroad by la Société Fabriques
de Produits Chimiques de Thann et de Mulhouse, of Thann, Alsace,) to be as
5 follows:-
In previous specifications it has been shewn that in the trinitrobutyltoluene and
trinitrobutylxylene manufactured under the name of artificial mask, for one nitro-
group may be substituted one of the following groups, halogen, cyanogen, ketonio
You go 2.1
without any essential alteration in the odour of the product. My foreign corres-
pondents have now found that the group azoimide shews a similar behaviour,
inasmuch as dinitrobutyltolyl-azoimide and dinitro-butyl-xylyl-azoimide are also
musk smelling substances.
The process of preparation of these substances by direct nitration of azoimido-
butyl-toluene CH, (CH) (CN)N, and azoimido-butyl-xylene CH₂ (CH,), (CHÂN,
gives unsatisfactory results.
My correspondents have therefore chosen the method described in the Specification
No. 15762 of 1895 and they have substituted in the dinitrobutyl toluidine (Berichte
der Deutschen chemischen Gesellschaft 24 Page 2839) and in the dinitrobutylxylidine
(Specification No. 15762 of 1895) for the amido-group the azoimido-group.
This can be done either by diazotisation of the said amines, transformation into
the perbromide, and treatment of the latter with ammonia, or by diazotisation of the
amines and farther treatment with hydrazoic acid.
It may be mentioned that the dinitrobutyl-xylidine can be prepared not only by
partial reduction of the trinitrobutylxylene, but also by nitration of the butylxylidine
which is prepared by the reduction of the crystallized nitrobutylxylene (Berichte der
Deutschen Cheinischen Gesellschaft xxiv. Page 2841).
For this purpose 10 parts of the butylsylidine are dissolved in 100 parts of mono-
hydrated sulphuric acid, and there are added at about 090. 8 parts of nitric acid of
100 per cent. dissolved in 50 parts of monohydrated sulphuric acid.
After a certain time the mixture is poured into water, the nitro-base is filtered and
crystallized from alcohol. By this way are obtained fine yellow needles, melting at
186°C. of dinitrobutyl-xylidine, identical with those obtained by the reduction of
trinitrobutylxylene.

page_text: The two following examples are typical for the preparation of the azoimides.
I. 100 grammes of dinitrobutylxylidine are dissolved in 2 kilo of concentrated
sulphuric acid of 66 Be the solution is cooled to 0° C and there are gradually added
25 to 30 grammes of dry and finely powdered sodium nitrite whilst stirring
continually. After a few hours the diazotisation is complete. The product is then
poured on to ice, and to the solution are added 225 grammes of bromine dissolved in
a concentrated solution of 150 grammes of bromide of potassium.
The perbromide thus formed is filtered rapidly, washed with water, and introduced
whilst wet, into a large excess of concentrated aqueous ammonia.
After about half an hour the reaction is complete.
It may be represented by the two following equations.
The azoimide filtered and crystallised from alcohol presents itself in the form of
white plates which melt at 89° C. are insoluble in water, soluble in alcohol, ether and
other organic solvents and have a strong odour of musk.
II. The dinitrobutylxylidine is diazotized in the same way as described above,
poured on to ice, and treated with a solution of 35 to 40 grammes of hydrazoate of
Bodium or a corresponding quantity of hydrazoic acid in aqueous solution. The
reaction takes place according to the following equation:
2
and is complete in a short time.
The azoiinide is then filtered and purified as before.
The dinitrobutyltolylazoimide is prepared in an identical way and has similar
properties melting at 146° C.
2

page_text: Improvements in the Manufacture of Artificial Musk.
I, OLIVER IMRAY, of Birkbeck Bank Chambers, Southampton Buildings, Chancery
Lane, in the County of London, Chartered Patent Agent, do hereby declare the
nature of this invention (as communicated to me from abroad by la Société
Fabriques de Produita Chimiques de Thann et de Mulhouse, of Thann, Alsace,) and in
what manner the same is to be performed, to be particularly described and
ascertained in and by the following statement :-
In previous specifications it has been shewn that in the trinitrobutyltoluene and
trinitrobutylxylene manufactured under the name of artificial musk, for one nitro-
group may be substituted one of the following groups, halogen, cyanogen, ketonic
CH.CO & aldehydio
without any essential alteration in the odour of the product. My foreign
correspondents have now found that the group azoimide shews a similar behavour
inasmuch as dinitrobutyltolyl-azoimide and dinitrobutyl-xylyl-nzoimide are also musk
smelling substances.
The process of preparation of these substances by direct nitration of azoimido-butyl-
toluene CH, (CH) (C,H,) N, and azoimido-butyl-xylene C.H, (CH), (CH) N, gives
unsatisfactory results.
"
My correspondents have therefore chosen the method described in the specification
No. 15762 of 1895 and they have substituted in the dinitrobutyl toluidine (Berichte
der Deutschen chemischen Gesellschaft 24 Page 2839) and in the dinitrobutylxylidine
(Specification No. 15702 of 1895) for the amido group the azoimido-group.
This can be done either by diazotisation of the said amines, transformation into the
perbromide, and treatment of the latter with ammonia, or by diazotisation of the
amines and farther treatment with hydrazoic acid.
It may be mentioned that the dinitrobutyl-xylidine can be prepared not only by.
partial reduction of the trinitrobutylxylene, but also by nitration of the butylxylidine
which is prepared by the reduction of the crystallized nitrobutylxylene (Berichte der
Deutschen Chemischen Gesellschaft xxiv page 2841). For this purpose 10 parts of
the butylxylidine are dissolved in 100 parts of monohydrated sulphuric acid, and
there are added at about 0° C. 8. parts of nitric acid of 100 per cent. dissolved in
50 parts of monohydrated sulphuric acid.
After a certain time the mixture is poured into water, the nitro-base is filtered and
crystallized from alcohol.
By this way are obtained fine yellow needles, melting at 186° C. of dinitrobutyl-
xylidine, identical with those obtained by the reduction of trinitrobutylxylene.
The two following examples are typical for the preparation of the azoimides I. 100
grammes of dinitrobutylxylidine are dissolved in 2 kilo of concentrated sulphuric
acid of 66 Bé. the solution is cooled to 0° C. and there are gradually added 25 to 30
grammes of dry and finely powdered sodium nitrite whilst stirring continually.
After a few hours the diazotisation is complete. The product is then poured on to
ice, and to the solution are added 225 grammes of bromine dissolved in a concentrated
solution of 150 grammes of bromide of potassium. The perbromide thus formed is
filtered rapidly, washed with water, and introduced whilst wet, into a large excess of
concentrated aqueous ammonia, After about half an hour the reation is complete,

page_text: The azoimide filtered and crystallised from alcohol presents itself in the form of
white plates which melt at 89° C. are insoluble in water, soluble in alcohol, ethe
and other organic solvents aud have a strong odour of musk.
II. The dinitrobutylxylidine is diazotised in the same way as described above,
poured on to ice, and treated with a solution of 35 to 40 grammes of hydrzante
of sodium or a corresponding quantity of hydrazoic acid in aqueous solution.
The reaction takes place according to the following equation:
and is complete in a short time.
The azoiinide is then filtered and purified as before.
The dinitrobutyltolylazoimide is prepared in an identical way and has similar
properties melting at 146° C.
Having now particularly described and ascertained the nature this inven-
tion and in what manner the same is to be performed, I declare that what I
claim is :-
1. The manufacture of dinitrobutyltolyl and dinitrobutyly lylazoimide, as
substitutes for inusk substantially as described.
1
2. The manufacture of dinitrobutylxylidine as a new materi for these musk
smelling bodies, by direct nitration of butylxylidine.
APEL & IMRAY,
Agents for the Applicant.