Manufacture of Ortho- and Para-nitrobenzylaniline Sulphonic Acids and their Homologues.
Year: 1898

page_text: Date of Application, 13th May, 1898
Complete Specification Left, 3rd Feb.. 1899-Accepted, 18th Mar., 1899
Manufacture of Ortho- and Para-nitrobenzylaniline Sulphonic Acids
and their Homologues.
I, OLIVER IMRAY, of Birkbeck Bank Chambers, Southampton Buildings, Chaucery
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:-
By the action of nitrobenzylchlorides or the mixture of nitrobenzylchloride
and nitrotoluene obtained by the partial chlorination of nitrotoluene upon the
sulphonic acids of aniline and its homologues are produced the nitrobenzylaniline-
sulphonic acids and their homologues, as described in the Specification No. 15890 of
1897.
This method produces excellent yields of faultless material, but with the drawback
that a rather expensive material is required namely aniline sulphonic acids which must
still be considered costly.
It is therefore to be considered whether the nitrobenzylanilinė sulphonic acid
could not be produced in a cheaper way by the sulphonation of nitrobenzylaniline,
since the latter bases may be manufactured easily and cheaply according to the
Specification No. 22041 of 1896.
The nitrobenzylanilines of the general formula:
after two points of attack to the acting sulphuric acid, that is to say, they can be
sulphonated just as well in the benzyl residue (1) as in the phenyl residue (II).
Which way the sulphonation would take place could not be foreseen. It was
clear, however, that the required products could only be obtained by sulphonation
of the phenyl residue II products which would yield nitrobenzaldehydes on oxidation,
whereas by sulphonation of the benzyl residue I products would be obtained
producing on oxidation the hitherto unknown sulphonic acids of nitrobenzaldehydes.
Experiments have proved that ortho- and para-nitrobenzylaniline and its homologues
may be sulphonated in the phenyl (amine) residue and consequently yield products
which when oxidised, as described in Specification No. 10689'96, easily produce
nitrobenzaldehydes.
The action of sulphuric acid and especially fuming acid upon nitrobenzylanilines
has to be started with great care, as otherwise a complete decomposition with
an explosive reaction may take place.
The nitrobenzylanilinės dissolve unchanged at first in an excess of sulphuric
acid (monohydrate). On heating this solution the greater part of the base becomes
transformed gradually into sulphonic acid; but to obtain a complete sulphonation,
a very considerable time is required. It is therefore advisable to operate with

page_text: a mixture of ordinary and fuming sulphuric acid, for instance in the following
manner.
85 kilos. of ortho- or para-nitrobenzylaniline (or the equimolecular quantity of a
homologous nitrobenzylbase) are dissolved in 170 kilos. of sulphuric acid
(monohydrate), to which are slowly run in at the temperature of the water bath
the calculated quantity of SO, in form of fuming sulphuric acid, in this case
therefore 52 kilos. of fuming sulphuric acid containing 60 per cent. of S.O,; the
sulphonation is complete in from 2 to 4 hours. The solution is allowed to cool
down and then diluted with about 1,000 kilos. of ice water, whereupon the
nitrobenzylaniline-sulphonic acid separates.
Filtration removes the greater part of the sulphonate from the mother lye, then
the raw nitrosulphonic acid is stirred with water and transformed in the usual
way into the calcium salt. The solution of the calcium salt is filtered from the
separated calcium sulphate and from the filtrate the nitrosulphonic acid is
precipitated by means of a diluted mineral acid.
In the same way there can be obtained the following nitrobenzyl-sulphonic
ABEL & IMRAY,
Agents for the Applicant.
CUMTIMIM DE MULLICATION.
Manufacture of Ortho- and Para-nitrobenzylaniline Sulphonic Acids
and their Homologues.
I, OLIVER IMRAY, of Birkbeck Bank Chambers, 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) and in what manner the sanie is to be performed
to be particularly described and ascertained in and by the following statement :-
By the action of nitrobenzylchlorides or the mixture of nitrobenzylchloride and
nitrotoluene obtained by the partial chlorination of nitrotoluene upon the sulphonic
acids of aniline and its homologues are produced the nitrobenzylaniline-sulphonic
acids and their homologues as described in the Specification No. 15890 of 1897.
This method produces excellent yields of faultless material, but with the
drawback that a rather expensive material is required namely aniline sulphonic
acids which must still be considered costly.

page_text: It is therefore to be considered whether the nitrobenzylanilinė sulphonic acid
could not be produced in a cheaper way by the sulphonation of nitrobenzylaniline,
since the latter bases may be manufactured easily and cheaply according to the
Specification No. 22041 of 1896.
The nitrobenzylanilines of the general formula:
offer two points of attack to the acting sulphuric acid, that is to say, they can he
sulphonated just as well in the benzyl residue (I) as in the phenyl residue (II).
.
Which way the-sulphonation would take place could not be foreseen.
It was clear, however, that the required products could only be obtained by
sulphonation of the phenyl residue II, products which would yield nitrobenzalde-
hydes on oxidation, whereas by sulphonation of the benzyl residue I products
would be obtained yielding on oxidation the hitherto unknown sulphonic acids of
nitrobenzaldehydes.
Experiments have proved that ortho- and para-nitrobenzylaniline and its
homologues may be sulphonated in the phenyl (amine) residue and consequently
yield products which when oxidised as described in Specification No. 10689 of
1896 easily produce nitrobenzaldehydes.
The action of sulphuric acid, and especially fuming acid upon nitrobenzyl-
anilines has to be started with great care as otherwise a complete decomposition
with an explosive reaction may take place.
The nitrobenzylanilines dissolve unchanged at first in an excess of sulphuric
acid (monohydrate). On heating this solution the greater part of the base becomes
transformed gradually into sulphonic acid; but to obtain a complete sulphonation,
a very considerable time is required.
It is therefore advisable to operate with a mixture of ordinary and fuming
sulphuric acid, for instance in the following manner.
85 kilos. of ortho- or para-nitrobenzylaniline (or the equimolecular quantity of a
homologous nitrobenzylbase) are dissolved in 170 kilos. of sulphuric acid (mono-
hydrate), to which are slowly run in at the temperature of the water bath the
calculated quantity of SO, in form of fuming sulphuric acid, in this case therefore
52 kilos. of funing sulphuric acid containing 60 per cent. of SO,; the sulphonation
is complete in from 2 to 4 hours. The solution is allowed to cool down and then
diluted with about 1,000 kilos. of ice water, whereupon the nitrobenzylaniline-
sulphonic acid separates.
Filtration removes the greater part of the sulphonic acid from the mother lye,
then the raw nitrosulphonic acid is stirred with water and transformed in the usual
way into the calcium salt. The solution of the calcium salt is filtered from the
separated calcium sulphate and from the filtrate the nitrosulphonic acid is
precipitated by means of a diluted mineral acid.
In the same way there can be obtained the following nitrobenzylsulphonic
acids:-
cids:-
o-nitrobenzyl-o-toluidinesulphonic acid from o-nitrobenzyl-o-toluidine.
p-
0-
P-
-0-
p-
-0-
-0-
"
"
"
"
p-
"
"
"
-P-
"
-0-
"
"
"
-p-
"
"
-p-
""
»-p-
32
-P-
0-
"
33
19
-p-
دو
"
"
-xylidine sulphonic acid
"
دو
-xylidine.

page_text: 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
claim is
1. The herein described manufacture of ortho- and para-nitrobenzylaniline-
sulphonic acids and their homologues by heating ortho- and para-nitrobenzyl-
aniline or their homologues with concentrated sulphuric acid or preferably with
fuming sulphuric acid and by separating the sulphonic acids, or their salts, thus
produced in the usual manner.
2. The products manufactured as above set forth.