Manufacture or Production of Aromatic Disulphonethylenediamides, Aromatic Disulphonpiperazides, and Piperazine.
Year: 1892

page_text: Date of Application, 13th Apr., 1892
Complete Specification Left, 12th Jan., 1893-Accepted, 13th Apr., 1893
PROVISIONAL SPECIFICATION.
Manufacture or Production of Aromatic Disulphonethylenediamides,
Aromatic Disulphonpiperazides, and Piperazine.
We, Dr. WILLY MARCKWALD of Kurfurstenstr. 111 Berlin, Germany, and
JULIUS FRIEDRICH HOLTZ of Mullerstrasse 170-71 Berlin, atoresaid, Director
of the Chemische Fabrik auf Actien, vorm. E. Schering, do hereby declare the
nature of this invention to be as follows:-
:-
This invention relates to a process for the manufacture or production of piperazine
in which an aromatic disulphonpiperazide RSON/CH, - CH,
1
CNSO,R is
CH, CH,
formed as an intermediate product, R in the above formula representing a hydro-
carbon residue CH, CHCH, or C10H,. This intermediate product can be
produced either directly or with the intermediate formation of aromatic disulpho-
ethylenediamide RSO, NHCH, CH, NH, SO,R; R having the
signification as above.
same
The process forming the subject of this invention and hereinafter described, is
based upon the fact that :-
1. The said aromatic disulphonethylenediamides are formed
(a) by the action of two molecules of an aromatic sulphochloride upon one
molecule of ethylenediamine;
(b) by the action of two molecules of an aromatic sulphoamide upon one
molecule of ethylenechloride or ethylenebromide.
2. The said aroinatic disulphonpiperazides are formed by the action of one
molecule of ethylenechloride or ethylenebromide upon the disulphonethylenedia-
mides obtained according to 1.
3. The aromatic disulphonpiperazides when heated with water and hydrochloric
acid or diluted or concentrated sulphuric acid to a high temperature, are split up
into the hydrocarbons (corresponding to the above mentioned hydrocarbon residues)
or their sulpho acids and into piperazine. In place of the aromatic sulphochlorides,
The sulpho-
the aromatic sulphobromides can be employed with the same success.
chlorides, -bromides, or -amides of the fatty series act in the same manner,
the use of the sulphochlorides or bromides of the fatty series on an industrial scale
is not advantageous on account of their high price and of the unpleasant properties
which they possess.
In carrying out this invention we proceed as follows:―
but
A. MANUFACTURE OF THE DISULPHONETHYLENEDIAMIDES.
Dibenzolsulphonethylenediamide.
(a). About 6 kilogs. of ethylenediamine and 8 kilogs. of sodic hydrate or
11-2 kilogs. of potassic hydrate are dissolved in 50 litres of water, and
This mixture,
35.7 kilogs. of benzolsulphochloride are added thereto.
whilst well agitated is heated to 80° C., and until the dibenzolsulphon-
ethylenediamide forms a friable solid mass. The liquid is then filtered off
and the residual mass is first washed with diluted hydrochloric acid, and
afterwards with water.
The dibenzolsulphonethylenediamide thus obtained is soluble in dilute
solution of caustic soda from which it can be precipitated by weak acids.
In the preceding process one molecule of ethylenediamine is used with
two molecules of an alkaline hydrate; but if three or four molecules of

page_text: alkaline hydrate be employed, the dibenzolsulphonethylenediamide is obtained
in solution from which it can be precipitated by hydrochloric acid.
) About 33-2 kilogs. of benzolsulphoamide and 37.6 kilogs. of ethylene-
bromide or 19-8 kilogs. of ethylenechloride are dissolved in 250 kilogs. of
96% alcohol, and, whilst the solution is boiling in the water bath on a
return cooler, 40 kilogs. of a 20% solution of caustic soda or 56 kilogs. of
a 20% solution of caustic potash are allowed to flow into it very gradually.
The heating is continued until the liquid has no longer any or only a very
weak alkaline reaction; then the alcohol is distilled off, the residue is
placed in a dilute solution of caustic soda, the solution is filtered, and from
the filtrate the dibenzolsulphonethylenediamide is precipitated by means
of hydrochloric acid.
stead of causing the solution of caustic alkali to flow in gradually, it may be
1 directly to the alcoholic solution, but the product obtained will not then be

page_text: separated hydrocarbon is removed from the solution and the latter is evaporated.
There is then obtained directly the acid sulphate salt of piperazine, which can be
treated to yield free piperazine by heating with a solution of caustic alkali or
with lime.
(b.) If in the preceding process the water, or the hydrochloric acid be replaced
by dilute sulphuric acid, the sulphuric acid is subsequently removed preferably by
means of lime, free piperazine being obtained in solution.
(c.) Instead of dilute sulphuric acid, a 80% to 100% solution of sulphuric acid
may be employed. In this case the operation may be effected in an open vessel
and the mixture need only be heated to a temperature of from about 180° to 200° C.
Besides piperazine, sulpho-acids of the hydrocarbons are also produced.
(d.) Finally the piperazide is dissolved in 4 to 8 parts of a 80% to 100% solution
of sulphuric acid, and into the solution, which is heated to 1408 to 150°°C., there
is passed superheated steam. By this means the hydrocarbon is distilled off.
Dated this 13th day of April 1892.
W. LLOYD WISE,
Per F. J. Brougham,
46, Lincoln's Inn Fields, London, W.C., Agent for the Applicants.
ATALINOO
DEBUIETUATION.
Manufacture or Production of Aromatic Disulphonethylenediamides,
Aromatic Disulphonpiperazides, and Piperazine.
We, Dr. WILLY MARCKWALD of Kurfurstenstrasse 111 Berlin, Germany, and
JULIUS FRIEDRICH HOLTZ of Mullerstrasse 170-71 Berlin, aforesaid, Director of
the Chemische Fabrik auf Actien, vorm. E. Schering, 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 primarily to the manufacture or production of piperazine
CH, CH₂
from an aromatic di-sulphonpiperazide RSON
-
CH, - CH₂/
NSO,R; R in
this formula representing a hydrocarbon residue C.H.; C.H.CH.; C¸H,(CH,),
or CH. This is effected according to this invention by causing water or a
mineral acid to act at a high temperature upon an aromatic di-sulphonpiperazide.
This latter substance can be produced either directly, or with the intermediate
formation of aromatic di-sulphonethylenediamide RSO, NHCH, CH, NH,
SO,R; R having the same signification as above.
The processes forming the subject of this invention and hereinafter described,
are based upon the fact that :-
1. The said aromatic di-sulphonethylenediamides are formed
(a) by the action of two molecules of an aromatic sulphochloride upon one
molecule of ethylenediamine;
(b) by the action of two molecules of an aromatic sulphonamide upon one
molecule of ethylenechloride or ethylenebromide.
2. The said aromatic di-sulphonpiperazides are formed,
(a) by the action of one molecule of ethylenechloride or ethylenebromide upon
the di-sulphonethylenediamides obtained according to 1; or
(b) by the action of two molecules of an aromatic sulphonamide upon two
molecules of ethylene chloride or ethylene-bromide.
3. The aromatic di-sulphonpiperazides when heated with water and hydrochloric
acid or diluted or concentrated sulphuric acid to a high temperature, are split up
into the hydrocarbons (corresponding to the above mentioned hydrocarbon residues)
or their sulpho acids and into piperazine.

page_text: In place of the aromatic sulphochlorides, the aromatic sulphobromides can be
aployed with the same success. The sulphochlorides, -bromides, or -amides of the
tty series act in the same manner, but the use of the sulphochlorides or bromides
the fatty series on an industrial scale is not advantageous on account of their high
ice and of the unpleasant properties which they possess.
In carrying out this invention we proceed as follows:-
A. MANUFACTURE OF THE AROMATIC DI-SULPHONETHYLENEDIAMIDES.
1. Di-benzenesulphonethylenediamide.
(a.) About 6 kilogs. of ethylenediamine and 8 kilogs. of sodic hydroxide
or 11.2 kilogs. of potassic hydroxide are dissolved in 50 litres of water,
and 35-7 kilogs. of benzenesulphochloride are added thereto. This mixture,
whilst well agitated is heated to 80° C., and until the di-benzenesulphon-
ethylenediamide forms a friable solid mass. The liquid is then filtered off
and the residual mass is first washed with diluted hydrochloric acid, and
afterwards with water.
The
di-benzenesulphonethylenediamide thus obtained is soluble in dilute
solution of caustic soda from which it can be precipitated by weak acids.
In the preceding process one molecule of ethylenediamine is used with two
molecules of an alkaline hydroxide; but if three or four molecules of alkaline
hydroxide be employed, the di-benzenesulphonethylenediamide formed is
held in solution by the excess of alkali from which it can be precipitated by
hydrochloric acid.
(b.) About 33-2 kilogs. of benzenesulphonamide and 37-6 kilogs. of ethylene-
bromide or 19.8 kilogs. of ethylenechloride are dissolved in 250 kilogs.
of 96% alcohol, and whilst the solution is boiling in the water bath on a
return cooler, 40 kilogs. of a 20% solution of caustic soda or 56 kilogs. of
a 20% solution of caustic potash are allowed to flow into it very gradually.
The heating is continued until the liquid has no longer any or only a very
weak alkaline reaction; then the alcohol is distilled off, the residue is placed
in a dilute solution of caustic soda, the solution is filtered, and from the
filtrate the di-benzenesulphonethylenediamide is precipitated by means of
hydrochloric acid.
nstead of causing the solution of caustic alkali to flow in gradually, it may be
ed directly to the alcoholic solution, but the product obtained will not then be
arge.
he following substances can be produced in an analogous manner :-
di-orthotoluenesulphonethylenediamide;
di-paratoluenesulphonethylenediamide;
di-xylenesulphonethylenediamide;
di-alphanaphthalenesulphonethylenediamide; and
di-betanaphthalenesulphonethylenediamide.
II. MANUFACTURE OF THE AROMATIC DI-SULPHONPIPERAZIDES.
.) About 34 kilogs. of di-benzenesulphonethylenediamide and 37.6 kilogs. of
lenebromide or 19.8 kilogs. of ethylenechloride are dissolved in 250 litres
6% alcohol, and heated in a return cooler; and 40 kilogs. of a 20% solution
austic soda or 56 kilogs. of a 20% solution of caustic potash are allowed to
into it very gradually. The heating is continued until the liquid has no longer
or only a very slight alkaline reaction. The mixture is then allowed to cool
the liquid is filtered from the residue which is then washed with alcohol, then
water, then with a hot dilute solution of caustic soda and finally again with 5
r.
e di-benzenesulphonpiperazide thus obtained remains behind as a white
er which is only soluble with difficulty in almost all of the ordinary dissolving
ts.

page_text: () Instead of producing the di-benzenesulphonpiperazide from the di-benzene-
sulphonethylenediamide, and thus as it were effecting the process in two stages, we
may also start directly with an aromatic sulphonainide such as benzenesulphonamide,
whereby we can effect the process in one stage.
In such case two molecules of ethylenechloride or ethylenebromide and four
molecules of an alkaline hydroxide are allowed to act upon two molecules of
benzenesulphonamide the reaction being effected in the manner hereinbefore
described.
The fall
L
III. MANUFACTURE OF PIPERAZINE.
(a.) About 10 kilogs. of di-benzenesulphon piperazide, or
10 kilogs. of di-paratoluenesulphonpiperazide, or
10 kilogs. of di-orthotoluenesulphonpiperazide, or
10 kilogs. di-xylenesulphonpiperazide, or
10 kilogs. di-alphanaphthalenesulphonpiperazide, or
10 kilogs. di-betanaphthalenesulphonpiperazide,
10
are heated with 50 kilogs. of water, or 50 kilogs. of a 10% to 20% solution of
hydrochloric acid in a digester for 6 hours to 200° to 250° C. After cooling the
separated hydrocarbon is removed from the solution and the latter is evaporated.
There is then obtained directly the acid sulphate salt of piperazine which can be
treated to yield free piperazine by heating with a solution of caustic alkali or with
lime.
(b) If in the preceding process (a) the water, or the hydrochloric acid be
replaced by dilute sulphuric acid, the sulphuric acid is subsequently removed,
preferably by means of lime, free piperazine being obtained in solution.
(c.) Instead of dilute sulphuric acid, a 80% to 100% solution of sulphuric
acid may be employed. In this case the operation may be effected in an open
vessel and the mixture need only be heated to a temperature of from about 180°
to 200° C. Besides piperazine, sulpho acids of the hydrocarbons are also
produced.
(d.) The piperazine may also be obtained by dissolving one part by weight of
an aromatic di-sulphonpiperazide mentioned under (a) in about 4 to 8 parts by
weight of sulphuric acid containing about 80 to 100% H,SO, and by introducing
superheated steam into this solution which is practically heated to about 140 to
150° C. The following reaction takes place :
R in this equation represents, as above stated, a hydrocarbon residue, such as
CH, CHCH, CH, (CH,), or C₁H,. By this reaction (.e. by the combination
45 of the said aromatic di-sulphonpiperazide with four molecules of water)
acid piperazine sulphate and the hydrocarbon corresponding to the said hydro-
carbon residue R contained in the treated aromatic di-sulphonpiperazide will be

page_text: naphthalenesulphochloride or alphanaphthalenesulphobromide, or betanaphthalene-
sulphochloride or betanaphthalenesulphobromide upon one molecule of ethylene-
diamine substantially as hereinbefore described.
Dated this 12th day of January 1893
W. LLOYD WISE,
Per F. J. Brougham,
46, Lincoln's Inn Fields, London, W.C., Agent for the Applicants.