Improvements in the Manufacture of Piperazine or Spermine.
Year: 1891

page_text: The decision of the Comptroller-General, of the 19th day of June 1893, allowed,
under Section 18 of the Patents, &c. Act, 1883, an Amendment of this
Specification.
Date of Application, 14th July, 1891
Complete Specification Left, 14th Apr., 1892-Accepted, 25th June, 1892
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of Piperazine or Spermine.
I, WILHELM MAJERT of 10 Madaistrasse, Berlin, Germany, Doctor of Chemistry,
'do hereby declare the nature of this invention to be as follows:-
According to the process described in the Specification of my Patent dated
29th September 1890 No. 15404, "piperazine" (which is a term to be preferred
for spermine or piperazidine) is produced by treating certain piperazine derivates
with alkali or earthy alkali bases.
Further experiments have however shown that the di-, tri-, and tetra-sulpho
acids of diphenyl-piperazine and ditolylpiperazine may be used instead of the
aforesaid piperazine derivates for producing the piperazine without otherwise
departing materially from process referred to.
Sulpho acids of diphenyl piperazine and of ditolyl-piperazine may suitably be
produced by means of fuming sulphuric acid or of anhydride of sulphuric acid.
All according to the amount of anhydride in the acid, the duration of the heating
and the temperature during the heating in the sulphonation I obtain di-, tri-, or
tetra-sulpho acids. It is advantageous for the production of the piperazine to apply
as many sulpho groups as possible. It is unnecessary for the production of the
piperazine to separate the several sulpho-acids.
The following sulpho-acids or their alkaline salts may for instance be produced
and applied for the purpose of the present invention viz..:
Diphenyl-piperazine-disulpho-acid
Diphenyl-piperazine-trisulpho-acid
Diphenyl-piperazine-tetrasulpho-acid
Orthoditolyl-piperazine-disulpho-acid
'Orthoditolyl-piperazine-trisulpho-acid
Orthoditolyl-piperazine-tetrasulpho-acid
Paraditolyl-piperazine-disulpho-acid
Paraditolyl-piperazine-trisulpho-acid
Paraditolyl-piperazine-tetrasulpho-acid
In order to produce the sulpho-acids especially if they are to be applied in the
present invention, it is suitable to put 1 part of diphenyl-piperazine or ditolyl-
piperazine (or their sulphate or hydrochlorate) in about 4 parts of fuming sulphuric
acid and to heat the mixture for some time, or I may also let the vapours of
anhydride of sulphuric acid act upon the finely divided diphenyl-piperazine or
ditolyl-piperazine or their aforesaid acid compounds and after that the most
'violent re-action is over, I heat the saine for some hours with fuming sulphuric
acid.
In order now to produce the piperazine the sulpho-acids are suitably put into the
alkaline salts in the usual manner and this dissolved in a stirring apparatus with
some water and about 4 parts alkali (soda or potash) for which may be partly or
wholly substituted earthy alkali bases (such as magnesia, lime, baryta or stroutian).

page_text: I then distil with steam as long as piperazine continues to pass over and treat the
latter further in the manner described in my aforesaid Patent Specification.
Dated this 14th day of July 1891.
JENSEN & SON,
77, Chancery Lane, London, W.C., Patent Agents.
COMPLETE SPECIFICATION (AMENDED).
Improvements in the Manufacture of Piperazine or a Form of
Spermine represented by C.HÂN,.
I WILHELM MAjert of 10 Madaistrasse Berlin, Germany, Doctor of Chemistry
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:-
According to the process described in the Specification of my Patent dated
29th September 1890 No. 15404 "piperazine" (which is a term to be preferred for
to "spermine" or "piperazidine" and is a form of spermine represented by CH₁₂)
is produced by treating certain piperazine derivates with alkali or earthy alkali
bases.
10
Further experiments have however shewn that the di-, tri-, and tetra-sulpho acids
of diphenyl piperazine and ditolylpiperazine may be used instead of the aforesaid
piperazine derivates for producing the piperazine without otherwise departing
materially from process referred to.
Sulpho acids of diphenyl-piperazine and of ditolyl piperazine may suitably be
produced by means of fuming sulphuric acid or of anhydride of sulphuric acid.
All according to the amount of anhydride in the acid, the duration of the heating
and the temperature during the heating in the sulphonation. I obtain di-, tri,- or
tetra-sulpho-acids. It is advantageous for the production of the piperazine to apply
as many sulpho groups as possible. It is unnecessary for the production of the
piperazine to separate the several sulpho-acids.
The following sulpho-acids or their alkaline salts may for instance be produced
and applied for the purpose of the present invention viz."
Diphenyl-piperazine-disulpho-acid,
Diphenyl-piperazine-trisulpho-acid,
Diphenyl-piperazine-tetrasulpho-acid,
Ortho ditolyl-piperazine-disulpho-acid,
Ortho ditolyl-piperazine-trisulpho-acid,
Ortho ditolyl-piperazine-tetrasulpho-acid,
Para ditolyl-piperazine-disulpho-acid,
Para ditolyl-piperazine-trisulpho-acid,
Para ditolyl-piperazine-tetrasulpho-acid.
In order to produce the sulpho-acids, especially if they are to be applied in the
present invention, it is suitable to put 1 part of diphenyl-piperazine or ditolyl-
piperazine (or their sulphate or hydrochlorate) in about 4 parts of fuming sulphuric
acid and to heat the mixture for some time; or I may also let the vapours of
anhydride of sulphuric acid act upon the finely divided diphenyl-piperazine or
ditolyl-piperazine or their aforesaid acid compounds, and after that the most violent
re-action is over, I heat the same for some hours with fuming sulphuric acid.
In order now to produce the piperazine the sulpho-acids are suitably put into the
alkaline salt in the usual manner and this dissolved in a stirring apparatus with
some water and about 4 parts alkali (soda or potash), for which may be partly or
wholly substituted carthy alkali bases (such as magnesia, lime, baryta or strontian),
I then distil with steam as long as piperazine continues to pass over and treat the
latter further in the manner described in my aforesaid Patent Specification.

page_text: 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:-
First. In the process for the manufacture of piperazine described in the Specifica-
tion of Patent dated 29th September 1890 No. 15404 the substitution as above
directed of di-, tri-, and tetrasulpho-acids of diphenyl-piperazine or of ortho- and
para-ditolyl-piperazine for the piperazine derivates named in the said Specification.
Second. The process for the manufacture of piperazine substantially as herein
described.
JENSEN & SON,
77, Chancery Lane, London, W.C., Patent Agents.