Manufacture of Monoacetyldiamidodiphenylaminesulphonic Acid and its Homologues.
Year: 1899

page_text: Date of Application, 9th Mar., 1899
Complete Specification Left, 4th Dec., 1899-Accepted, 6th Jan., 1900
PROVISIONAL SPECIFICATION.
Manufacture of Monoacetyldiamidodiphenylaminesulphonic Acid
and its Homologues.
I, OLIVER IMRAY, of Birkbeck Bank Chambers, Southampton Buildings, in the
County of London, Chartered Patent Agent, do hereby declare the nature of this
invention (as communicated to me from abroad by The Farbwerke vormals: Meister
Lucius and Brüning, of Hoechst a/Main, in the Empire of Germany, Chemical
Manufacturers,) to be as follows:-
Diamidodiphenylaminesulphonic acid is obtained according to the German Patent
No. 86250 by the action of para-phenylenediamine upon nitro-chlorobenzenesulphonic
acid and then by boiling the aqueous solution of the mixture with sodium acetate
and reducing the condensation product thus obtained.
Experiments to obtain the acetyl-compound of the acid by this method, namely,
to condense acetyl-para-phenylenediamine with nitrochlorobenzene-sulphonic acid
under conditions stated in the said Patent Specification do not succeed, as on boiling
the aqueous solution with sodium acetate no condensation whatever takes place and
on boiling it with sola, there is only a partial condensation which does not lead to
the desired products, but to the acid of the German Patent No. 86250.
The acetyl
group is therefore split off in the latter case and the paraphenylenediamine reacts
with the nitrochlorobenzenesulphonic acid. It could therefore not be expected that
the nitrochlorobenzenesulphonic acid would condense with acetyl-para-phenylenediamine
to form a stable diphenylamine derivative, considering the easy hydrolysis of acetyl-
para-phenylenediamine.
My foreign correspondents have found, however, that this result may be obtained
in a satisfactory mauner by operating at a high temperature in a closed vessel ander
pressure.
EXAMPLE.
2.60 kilos. of sodium para-nitrochlorbenzene-o-sulphonate are dissolved hot with
1.51 kilo. of acetyl para-phenylenediamine and 1.36 kilo. of sodium acetate with
about 20 litres of water, the whole being heated to 150° C. in a closed vessel
provided with an agitator. A yellow solution results which is not precipitated by
acetic acid, and thus differs from the not acetylated nitro acid described in the
German Patent Specification No. 86250.
The solution of acetyl-para-amido-para-nitrodiphenylamine-ortho-sulphonic acid
thus obtained may be isolated, by salting out, as a resinous precipitate which
crystallises with difficulty. It is, therefore, preferable, considering the difficulty in
manipulating this body, to reduce the yellow solution directly to the corresponding
amido-acid.
The reduction succeeds best with zinc dust and acetic acid or with iron and acetic
acid. The product of reduction is dissolved in soda the solution is filtered and the
filtrate is acidified with acetic acid, when the acetyl-diamidodiphenylamine-ortho-
sulphonic acid separates in small crystals which on the cooling of the liquid are
pressed and dried.

page_text: If, in this example for the acetyl-para-phenylenediamine be substituted the
equivalent quantity of substituted acetyl-para-phenylenediamine, such as acetyl-
para-toluylenediamine, acetyl-methoxy-or
ethoxy-para-phenylenediamine,
etc.,
the corresponding substituted acetyl-diamidodiphenylaminesulphonic acids are
obtained.
The acetyldiamidodiphenylaminesulphonic acid and its substitution products
obtained by this process may be employed for the manufacture of dyestuffs; it
serves also particularly for practically obtaining diamidodiphenylamine-sulphonic
acid and its substitution products as described in the German Patent Specification
No. 86253, as the acetyl group may be easily eliminated by hydrolysis.
The acetyldiamidodiphenylaminesulphonic acid may be diazotised and combined
with suitable bodies leading thus to a series of new azo-dyestuffs.
On elimination of the acetyl-group from these azo-dyestuffs, another series of new
dyestuffs may be obtained which are characterized by their still containing an amido-
group and on further diazotisation and combination lead to a third series of new
mixed azo-dyestuffs.
Dated this 9th day of March 1899.
ABEL & IMRAY,
Agents for the Applicant.
Manufacture of Monoacetyldiamidodiphenylaminesulphonic Acid
and its Homologues.
I, OLIVER IMRAY, of Birkbeck Bank Chambers, Southampton Buildings, in the
County of London, Chartered Patent Agent, do hereby declare the nature of this
invention (as communicated to me from abroad by The Farbwerke vormals Meister
Lucius and Brüning, of Hoechst a/Main, in the Empire of Germany, Chemical
Manufacturers) and in what manner the same is to be performed, to be particularly
described and ascertained in and by the following statement:—
Diamidodiphenylaminesulphonic acid is obtained according to the German l'atent
No. 86,250 by the action of para-phenylenediamine upon nitro-chloro-benzenesulphonic
acid and then by boiling the aqueous solution of the mixture with sodium acetate
and reducing the condensation product thus obtained.
Experiments to obtain the acetyl-compound of the acid by this method, namely, to
condense acetyl-para-phenylenediamine with nitrochlorobenzenesulphonic acid under
conditions stated in the said Patent Specification do not succeed, as on boiling the
aqueous solution with sodium acetate no condensation whatever takes place and on
boiling it with soda, there is only a partial condensation which does not lead to the
desired products, but to the acid of the German Patent No. 86,250. The acetyl
group is therefore split off in the latter case and the paraphenylenediamine reacts
with the nitrochlorobenzenesulphonic acid.
It could therefore not be expected that the nitrochlorobenzenesulphonic acid
would condense with acetyl-para-phenylenediamine to form a stable diphenylamine
derivative, considering the easy hydrolysis of acetyl-para-phenylenediamine.
My foreign correspondents have found, however, that this result may be obtained
in a satisfactory manner by operating at a high temperature in a closed vessel under
pressure.

page_text: about 20 litres of water, the whole being heated to 150° C. in a closed vessel provided
with an agitator. A yellow solution results which is not precipitated by acetic acid,
and thus differs from the not acetylated nitro acid described in the German Patent
Specification No. 86,250.
acid
The solution of acetyl-para-amido-para-nitrodiphenylamine-ortho-sulphonic
thus obtained may be isolated, by salting out, as a resinous precipitate which
crystallises with difficulty. It is, therefore, preferable considering the difficulty in
manipulating this body, to reduce the yellow solution directly to the corresponding
amido-acid.
The reduction succeeds best with zine dust and acetic acid or with iron and acetic
acid. The product of reduction is dissolved in soda, the solution is filtered and the
filtrate is acidified with acetic acid, when the acetyl-diamidodiphenylamine-ortho-
sulphonic acid separates in small crystals which on the cooling of the liquid are
pressed and dried.
the
If, in this example, for the acetyl-para-phenylenediamine be substituted the
equivalent quantity of substituted acetyl-para-phenylenediamine, such as acetyl-para-
toluylenediamine, acetyl-methoxy or ethoxy-para-phenylenediamine, etc.,
corresponding substituted acetyl-diamidodiphenylamine-sulphonic acids are obtained.
The acetyldiamidodiphenylaminesulphonic acid and its substitution products
obtained by this process may be employed for the manufacture of dyestuff's; it serves
also particularly for practically obtaining diamidodiphenylaminesulphonic acid and its
substitution products as described in the German Patent Specification No 86,250, as
the acetyl group may be easily eliminated by hydrolysis.
The
acetyldiamidodiphenylamine-sulphonic acid may be diazotised and combined
with suitable bodies leading thus to a series of new azo-dyestuffs.
On elimination of the acetyl-group from these azo-dyestuffs, another series of new
dyestuffs may be obtained which are characterised by their still containing an amido-
group and on further diazotation and combination lead to a third series of new mixed
azo-dyestuffs.
Having now particularly described and ascertained the nature of this invention and
in what manner the same is to be performed, I declare that what I clain is :-
The herein described manufacture of acetyl-p-diamidodiphenylaminesulphonic acid
and its homologues, by heating acetyl-p-phenylenediamine and its homologues with
p-nitrochlorobenzene-o-sulphonic acid in a closed vessel to about 150° C. in presence
of agents capable of absorbing hydrochloric acid and by reducing the condensation
products thus formed, substantially as described.
Dated this 4th day of December 1899.
ABEL & IMRAY,
Agents for the Applicant.