Manufacture of Hydroxylamine, Hydrazine, and Derivatives .thereof.
Year: 1894

page_text: Date of Application, 9th June, 1894
Complete Specification Left, 6th Mar., 1895-Accepted, 20th Apr., 1895
PROVISIONAL SPECIFICATION.
Manufacture of Hydroxylamine, Hydrazine, and Derivatives
.thereof.
I, Dr. ALFRED WOHL of No. 5 Joachimsthaler Strasse, Berlin, Germany,
Chemist do hereby declare the nature of this invention to be as follows:-
This invention relates to the production of hydroxylamine, hydrazine and
derivatives thereof from certain nitrogen-oxygen compounds such as nitrates,
nitrites and ethers of nitric and nitrous acid, nitro derivatives of the fat or
aromatic series, nitroso compounds, nitramines nitrosamines and the like.
These bodies may be reduced under suitable conditions to substances of the
kind mentioned in the title. Hitherto this could not be done or could be done
only in such an imperfect manner that a manufacture of these substances was
almost entirely impracticable.
By the present invention the substances referred to can be manufactured on a
large scale, these substances forming reagents of great technical value.
My process consists in effecting the reduction of the nitrogen-oxygen compound
by means of finely suspended metals not, as has hitherto been the usual method,
in an alkaline or acid solution, but in a neutral solution; in several cases also,
the presence of a neutral salt (such as for instance chloride of sodium, calcium
and the like) is required in order to render the reaction more .complete and to
secure a good yield.
According to the nature of the nitrogen-oxygen compounds used the reaction
takes place in the following manner.
1. Hydroxylamine and derivatives thereof are formed by applying the process
to nitrates, nitrites, the ethers of nitric and nitrous acids, nitro compounds and
nitroso compounds as may be illustrated by the following typical equations, in
which Me indicates a metal, and X an organic radical:
N. NO,
N NO, X-N-NO, X-N-NO,
X.
X
N. NO
N. NO
X
and the corresponding final products obtained therefore possess the following
constitution:

page_text: Pb (NO)2 + 6 Pb + 10 H₂O = 7 Pb (OH), + 2 NH₂OH
in cold solution; if the temperature is raised to 60°-80° the reaction is completed
in a shorter time.
The hydroxylamine obtained in this way is free from ammonia, the solution is
filtered off and the hydroxylamine may be transformed into its salts, or employed
directly.
2. 100 kilos. nitrobenzol and 10 kilos. potassium chloride are dissolved in
400 litres of diluted alcohol at 60°. To this solution 150 kilos. of zinc powder
are added during about 20 minutes. To complete the reaction, the solution is
boiled for some minutes, afterwards filtered off and concentrated to an oily
consistence. In this manner about 75 to 80 per cent. of nearly pure phenyl-
hydroxylamine are obtained. I wish it to be understood that I do not claim the
process for the production of phenylhydroxylamine without addition of neutral
salts as this has been described by Bamberger (Berl. Ber. XXVII, 1348).
3. Nitrosodiphenylamine (CH), N NO, treated with metal and water, readily
yields the hydrazine (CH), N NH,.
Dated this 9th day of June 1894.
:
ABEL & IMRAY,
Agents for the Applicant.
Manufacture of Hydroxylamine, Hydrazine, and Derivatives
thereof.
I, Dr. ALFRED WOUL, of No. 5 Joachimsthaler Strasse, Berlin, Germany,
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 :-
This invention relates to the production of hydroxylamine, hydrazine and
derivatives thereof from certain nitrogen-oxygen compounds, such as nitrates,
nitrites and ethers of nitric and nitrous acid, nitro derivatives of the fat or
aromatic series, nitroso compounds, nitramines, nitrosamines &c.
These bodies may be reduced under suitable conditions to substances of the
kind mentioned in the title. Hitherto this could not be done, or could only be
done in such an imperfect manner that a manufacture of these substances was
almost entirely impracticable.
By the present invention the substances referred to can be manufactured on a
large scale, these substances forming reagents of great technical value.
My process consists in effecting the reduction of the nitrogen-oxygen compound
by means of finely suspended metals not, as has hitherto been the usual method,
in an alkaline or acid solution but in a neutral solution; in several cases also, the
presence of a neutral salt (such as for instance chloride of sodium, or of calcium
and the like) is required in order to render the reaction more complete and to
secure a good yield.
According to the nature of the nitrogen-oxygen compounds used the reaction
takes place in the following manner.
1.) Hydroxylamine and derivatives thereof are formed by applying the process
to nitrates, nitrites, the ethers of nitric and nitrous acids, nitro compounds and

page_text: nitroso compounds as may be illustrated by the following typical equations in
which Me indicates a metal, and X an organic radical.

page_text: treated with metal and water, reauny yietus
the bydrazine (C.H.), N NH,.
EXAMPLE 9.
In order to prepare hydroxylamine-amyl-ether, 30 parts of amyl nitrite and
2 parts of calcium chloride are dissolved in 100 parts of amyl alcohol. To the
boiling solution 40 parts of zinc powder are added, and the boiling is continued
till the amyl nitrite disappears. The hydroxylamine-amyl-ether is isolated in
form of its benzylidene-compound.
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 mauufacture of hydroxylamine, hydrazine and their

page_text: derivatives by moderate reduction of nitrogen-oxygen compounds by means of
finely suspended metals in neutral solution with or without addition of neutral
salts.
2. The products manufactured as above set forth.
11
A
1
100%
ABEL & IMRAY,
Agents for the Applicant.