Manufacture of Ortho- and Para-nitrobenzylaniline Sulphonic Acids and their Homologues.
Year: 1897

page_text: Date of Application, 3rd July, 1897
Complete Specification Left, 4th Apr., 1898-Accepted, 28th May, 1898
PROVISIONAL SPECIFICATION.
Manufacture of Ortho- and Para-nitrobenzylaniline Sulphonic Acids
and their Homologues.
I, OLIVER IMRAY, of No. 28, Southampton Buildings, Chancery Lane, 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 :-
In the application for Patent No. 22041 of 1896 is described a method permitting
an indirect separation of the mixtures obtained from o-nitrobenzylchloride and
o-nitrotoluene or p-nitrobenzylchloride and p-nitrotoluene respectively by direct
chlorination of ortho and para-nitrotoluene.
This method, briefly stated, consists in allowing aniline or its homologues, with or
without addition of alkalies, to act upon the said chlorination mixtures; in this
manner mixtures are obtained such for instance as nitrobenzylaniline, nitrotoluene
and hydrochloride of aniline, their separation being easily effected by taking advantage
of their various chemical and physical properties: Thus, on the one hand, is obtained
the whole of the nitrobenzylchloride contained in the chlorination mixture in form of
nitrobenzyl aniline or its homologues; and, on the other hand, the non-chlorinated
nitrotoluene in a pure state; the two bodies are consequently in condition to be
directly applicable in chemical industry.
My foreign correspondents have found that the same result is arrived at by a some-
what more simple and convenient method.
If, for instance, an aniline sulphonic acid or a homologue thereof, is allowed to act,
under appropriate conditions, upon the product of reaction of chlorine or bromine on
ortho- or para-nitrotoluene containing about 50 per cent. of chloride or bromide,. a
reaction takes place according to the following formula:-
8
(SO,Na
+ NaOH=
NH₂
NO-CH-CH₂Cl+CH
the 50 per cent..
product of reaction
of chlorine or bro-
mine upon o- or p-
nitrotoluene.
No₂
"CH,NH.CH SO,Na
NaCl + H₂O+CH₁
+CH₁
сн
ΝΟ

page_text: that is to say, the alkaline salt of o- or p-nitrobenzylaniline sulphonic acid is obtained,
which, as it is soluble in water, is easily and entirely separated from the o- or p-nitro-
toluene insoluble in water, the latter may serve at once for another chlorination or
bromination.
The process may be conducted in the following manner :-
34-2 kilos. of a 50 per cent. raw chlorination of o- or p-nitrotoluene, corresponding
to 17.1 kilos. of nitrobenzylchloride, or the equivalent quantity of a bromination of
equal percentage, are gently boiled for several hours, in a vessel provided with an
agitator and an inverted condenser, together with a solution of 23.3 kilos. of sul-
phanilate of sodium (83.5 per cent.) and 6 kilos. of calcined soda in 100 litres of
water. The whole is allowed to cool and the aqueous solution of the sodium salt of
nitrobenzylsulphanilic acid thus formed is separated, whilst the nitrotoluene, again
obtained, remains behind and may serve anew for chlorinating or brominating.
The free nitrobenzylsulphanilic acid is precipitated from the aqueous solution with
diluted mineral acids, then filtered off, pressed and dried.
In the above example, for the sulphanilic acid may be substituted other aniline
sulphonic acids or their homologues in equivalent quantity and in particular by the
following:
or by a mixture of two or more of the said sulphonic acids.
The series of homologues of o- and p-nitrobenzylaniline sulphonic acids are thus 30
obtained.
For the soda may be substituted other fixed alkali, alkali carbonate or acetate or
alkaline earths.
ABEL & IMRAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Manufacture of Ortho- and Para-nitrobenzylaniline Sulphonic Acids
and their Homologues.
I, OLIVER IMRAY, of Birkbeck Bank Chambers, Southampton Buildings, but 40
formerly of 28, Southampton Buildings, Chancery Lane, in the County of London,
Chartered Patent Agent, do hereby declare the nature of this invention, (which has
been communicated to me from abroad by The Farbwerke vormals: Meister Lucius

page_text: and Brüning, of Hoechst a/Main, in the Empire of Germany, Chemical Manufac-
turers) and in what manner the same is to be performed to be particularly described
and ascertained in and by the following statement :--
In the application for Patent No. 22041 of 1896, is described a method permit-
ting an indirect separation of the mixtures o-nitrobenzylchloride and o-nitrotoluene
or p-nitrobenzylchloride and p-nitrotoluene respectively obtained by direct chlori-
nation of ortho- and para-nitrotoluene.
This method, briefly stated, consists in allowing aniline or its homologues, with or
without addition of alkalies, to act upon the said chlorination mixtures; in this
manner mixtures are obtained such for instance as nitrobenzylaniline, nitrotoluene
and hydrochloride of aniline, their separation being easily effected by taking
advantage of their various chemical and physical properties.
Thus, on the one hand is obtained the whole of the nitrobenzylchloride contained
in the chlorination mixture in form of nitrobenzylaniline or its homologues; and, on
the other hand, the non-chlorinated nitrotoluene in a pure state; the two bodies are
consequently in condition to be directly applicable in chemical industry.
.
My foreign correspondents have found that the same result' is arrived at by a
somewhat more simple and convenient method.
If, for instance, an aniline-sulphonic acid or a homologue thereof, is allowed to
act, under appropriate conditions, upon the product of reaction of chlorine or bromine
on ortho- or para-nitrotoluene containing about 50 per cent. of chloride or bromide,
a reaction takes place according to the following formula:-
o- or p-nitrotoluene
o- or p-nitrobenzylaniline-
sulphonic acid
that is to say, the alkaline salt of o- or p-nitrobenzylaniline-sulphonic acid is
obtained, which, as it is soluble in water, is easily and entirely separated from the
oor p-nitrotoluene insoluble in water; the latter may serve at once for another
chlorination or bromination.
The process may be conducted in the following manner :-
34.2 kilos. of a 50 per cent. raw chlorination of o- or p-nitrotoluene, corresponding
to. 171 kilos. of nitrobenzylchloride, or the equivalent quantity of a bromination of
equal percentage, are gently boiled for several hours, in a vessel provided with an
agitator and an inverted condenser, together with a solution of 23-3 kilos. of
sulphanilate of sodium (83.5 per cent.) and 6 kilos. of calcined soda in 100 litres of
water. The whole is allowed to cool and the aqueous solution of the sodium salt
of nitrobenzylsulphanilic acid thus formed is separated, whilst the nitrotoluene, again
obtained, remains behind and may serve anew for chlorinating or brominating.
The free nitrobenzylsulphanilic acid is precipitated from the aqueous solution, with
diluted mineral acid, then filtered off, pressed and dried.
In the above example, for the sulphanilic acid may be substituted other aniline-

page_text: Dated the 4th day of April 1898.
ABEL & IMRAY,
Agents for the Applicant.