Production of Sodium-formylphenylhydrazine and of Symmetric Alkylphenylhydrazine and of Analogous Compounds.
Year: 1890

page_text: Date of Application, 8th Nov., 1890
Complete Specification Left, 6th Aug., 1891-Accepted, 12th Sept., 1891
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBWERKE VORMALS MEISTER LUCIUS
AND BRUNING, of Hoechst-am-Maine, in the Empire of Germany.]
Production of Sodium-formylphenylhydrazine and of Symmetric
Alkylphenylhydrazine and of Analogous Compounds.
I, OLIVER IMRAY, of No. 28 Southampton Buildings, Chancery Lane, in the
County of London, Fellow of the Institute of Patent Agents, do hereby declare the
nature of this invention to be as follows:-
Hitherto the use of symmetric alkylhydrazine for technical purposes was barred
by the high price asked for them in consequence of the difficulties attending their
preparation.
As is well known, secondary bases are quite easily obtained in the aniline
series.
These bases form gently in the action of alkylhalogenides upon the sodium
compounds of the anilides, as for example, sodium-acetanilide.
In order to prepare secondary alkylphenylhydrazines, sodium has been caused to
act upon phenylhydrazine, and the sodium compounds have been treated with alkyl-
halogenides. But, in this way, only unsymmetric alkylphenylhydrazines could be
prepared; the sodium acting directly upon phenylhydrazine entering in the first
stage into the imide group of the phenylhydrazine and thereby forming the
body C.H,NNaNH,, from which only unsymmetric alkylphenylhydrazines can be
derived If, however, the sodium is caused to act upon formylphenylhydrazine, it
takes the place of a hydrogen atom of the amide group; that is to say, by the
action of sodium upon formylphenylhydrazine there is formed sodium-formylphenyl-
hydrazine of the constitution: CHÊNHN
CHO
,
Na from which body is obtained
by the action of chloro-cromo- or iodo-alkyl the symmetric alkylphenylhy-
drazine.
In this way, the reaction proceeds in two stages, that is to say :-
1. The action of sodium upon formylphenylhydrazine
C.H. NH. NHCHO.+Na=H+CH. NH, NCHO. Na.
2. The action of alkylhalogenides upon sodium formylphenylhydrazine: for
example:
CH.. NH. NCHO.Na+TCH,=TNa+CH_NH.N
CHỤ
CH,
By saponifying the formyl compound is obtained the free symmetric alkylphenyl-
ydrazine. For the formylphenylhydrazine may be substituted in like manner
cetylphenylhydrazine, oxalyldiphenylhydrazine or another such compound.
My foreign correspondents operate as in the following example:
Formylphenylhydrazine (obtained by boiling phenylhydrazine with formic acid)
dissolved in xylol and then boiled with the calculated quantity of sodium. The
quid soon assumes the form of a crystalline paste of sodium-formylphenyl-
ydrazine.
This body in a dry state is so very explosive that it cannot be isolated. To the
ixture of this body in xylol is added the calculated at th
CgH.. NH. NCHO. Na+TCH=TNa+CH.NH.N
CHU
CH,
By saponifying the formyl compound is obtained the free symmetric alkylphenyl-
hydrazine. For the formylphenylhydrazine may be substituted in like manner
acetylphenylhydrazine, oxalyldiphenylhydrazine or another such compound.
My foreign correspondents operate as in the following example:
Formylphenylhydrazine (obtained by boiling phenylhydrazine with formic acid)
is dissolved in xylol and then boiled with the calculated quantity of sodium. The
quid soon assumes the form of a crystalline paste of sodium-formylphenyl-
Hydrazine.
This body in a dry state is so very explosive that it cannot be isolated. To the
mixture of this body in xylol is added the
calculated
lated quantity of iodemethyl
After disappearance of the iodo-methyl, the mixture is filtered and the xylol is
distilled off; afterwards the formyl compound is saponified in the usual way by
[Price 6d.1

page_text: means of acids or alkalies and from the alkaline liquid the symmetric methylphenyl-
hydrazine is taken up with ether. From the filtered ether solution the ether is
completely removed by distillation on a water bath, while a stream of dry hydrogen
is passed through the solution; the oil remaining afterwards is purified by
distillation'in vacuo.
Symmetric methylphenylhydrazine presents itself in the form of a yellowish oil,
having its boiling point under ordinary pressure at from 220° to 230° C. By
oxidation with oxide of mercury it is converted into azophenylmethyl.
When in the above reaction for the halogen methyl is substituted halogen ethyl,
the symmetric ethyl-phenylhydrazine is obtained. This body is identical in every
respect with the one already known (Beilstein 2nd edition vol. 3 p. 940).
Dated this 8th day of November 1890.
ABEL & IMRAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Production of Sodium-formylphenylhydrazine and of Symmetric
Alkylphenylhydrazine and of Analogous Compounds.
I, OLIVER IMRAY of No. 28 Southampton Buildings, Chancery Lane, in the
County of London, Fellow of the Institute of Patent Agents, do hereby
declare the nature of this invention and in what manner the same is to be per-
formed to be particularly described and ascertained in and by the following
statement:—
Hitherto the use of symmetric alkylhydrazines for technical purposes was barred
by the high price asked for them in consequence of the difficulties attending their
preparation.
As is well known, secondary bases are quite easily obtained in the aniline-
series. These bases form gently in the action of alkylhalogenides upon the
sodium compounds of the anilides, as for example, sodium-acetanilide.
In order to prepare secondary-alkylphenylhydrazines, sodium has been caused to
act upon phenylhydrazine and the sodium compounds have been treated with
alkylhalogenides. But, in this way, only unsymmetric alkylphenylhydrazines
could be prepared, the sodium acting directly upon phenylhydrazine entering in
the first stage into the imide group of the phenylhydrazine and thereby forming the
body CH NNa. NH2, from which only unsymmetric alkylphenylhydrazines can be
derived. If however the sodium is caused to act upon formylphenylhydrazine, it
takes the place of a hydrogen atom of the amide-group; that is to say by the action
of sodium upon formylphenylhydrazine there is formed sodium formylphenyl-
CHO
hydrazine of the constitution: CH.NH.N:
Na ,
from which body is obtained
by the action of chloro-bromo or iodo-alkyl the symmetric alkylphenylhydrazine.
In this way the reaction proceeds in two stages, that is to say.
1. The action of sodium upon formylphenylhydrazine.
CH.NH.NHCHO+Na=H+CH NH.NCHO. Na.
2. The action of alkylhalogenides upon sodium-formylphenylhydrazine: for
example.
CH.NH.NCHO. Na+TCH,=TNa+CH.NH.N
CHO
By saponifying the formyl compound is obtained the free symmetric alkylphenyl-
hydrazine.
For the formylphenylhydrazine may be substituted in like manner acetylphenyl-
hydrazine, oxalyldiphenylhydrazine or another such compound.

page_text: My foreign correspondents operate as in the following example: Formylphenyl-
hydrazine (obtained by boiling phenylhydrazine with formic acid) is dissolved in
xylol and then boiled with the calculated quantity of sodium. The liquid soon
assumes the form of a crystalline paste of sodium formylphenylhydrazine. This
body in a dry state is so very explosive that it cannot be isolated. To the
mixture of this body in xylol is added the calculated quantity of indomethyl.
After disappearance of the iodo-methyl, the mixture is filtered and the xylol is
distilled off; afterwards the formyl compound is saponified in the usual way by
means of acids or alkalies and from the alkaline liquid the symmetric methyl-
phenylhydrazine is taken up with ether. From the filtered ether solution the
ether is completely removed by distillation on a water bath, while a stream of
dry hydrogen is passed through the solution; the oil remaining afterwards is
purified by distillation in vacuo. Symmetric methylphenylhydrazine presents
itself in the form of a yellowish oil, having its boiling point under ordinary
pressure at from 220 to 230° C. By oxydation with oxide of mercury it is
converted into azophenylmethyl.
When in the above reaction for the halogenmethyl is substituted halogen-ethyl,
the symmetric ethyl-phenylhydrazine is obtained. This body is identical in every
respect with the one already known (Beilstein 2nd edition vol. 3, p. 940).
Having now particularly described and ascertained the nature of my said
invention and in what manner the same is to be performed, I declare that what
I claim is :-
1. The herein described process for producing sodium-formylphenylhydrazine by
the action of sodium upon formylphenylhydrazine.
2. As a new product the sodium formylhydrazine above referred to.
3. The herein described process for producing symmetric methyl- and ethyl-
phenylhydrazine by the action of halogen-methyl and ethyl respectively upon
sodium-forinylphenylhydrazine, sodium acetylphenylhydrazine, or sodium oxalyl-
liphenylhydrazine, and saponification of the product resulting from this reaction.
4. As new products the symmetric methyl and ethyl phenylhydrazines above
referred to.
Dated this 6th day of August 1891.
ABEL & IMRAY,
Agents for the Applicant.