Year: 1896

page_text: 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 to
be as follows:-
According to the researches of Wachendorff, Haeusermann and Beck, Loesner and
others, the corresponding nitrobenzyl chloride or nitrobenzyl-bromide of the general
formula C,H, {CH₂X (where X represents the halogen atom,) is obtained by the
action of chlorine or bromine, with or without application of the so called "carriers of
halogen," upon o- or p-nitrotoluene at a high temperature.
A quantitative chlorination or bromination of the two nitro-toluenes into nitrobenzyl
chloride or bromide is however not possible in this way, as a prolonged action of the
halogen produces partly ring-substitution-compounds and partly products of condensa-
tion of complicated composition, besides the desired nitrobenzyl chloride or
bromide.
With an appropriate choice of working conditions, 50 per cent. and more of the
nitrotoluene employed may be transformed into the corresponding nitrobenzyl haloid,
without producing any considerable quantity of the said by-product.
The close relationship between the o- and p- nitrobenzyl haloids and the chemistry of
indigo and triphenylmethane dyestuffs having become known by the fundamental
researches of A. Baeyer and E. & O. Fischer, colour manufacturers soon entered this
promising field, and attempts have not been wanting, within the last 10 years, to
arrive at the separation of the pure nitrobenzyl haloid from the said raw chlorination
or bromination products.
A satisfactory solution of this problem is still unknown.
By the action of aniline or its homologues upon the nitrobenzyl haloids, the
nitrobenzyl bases of the general formula: CH-NH-CH-CH,NO, are obtained.
My foreign correspondents having found that the nitrobenzyl bases can easily be
transformed by oxidation into the corresponding nitrobenzylidene compounds of the
general formula:CH-N=CH-CH-NO, which latter compounds are split up
by diluted mineral acids into amido bases and nitrobenzaldehyde, the problem of
separating the pure nitrobenzylchloride from the above mentioned raw chlorination or
bromination product began to be of renewed interest for them.
They succeeded in carrying out this separation in a practicable manner by indirect

page_text: means, namely, by obtaining the pure nitrobenzyl bases from the raw chlorination or
bromination products of the two nitrotoluenes.
The invention may be characterized in the following way :-
By means of incomplete chlorination or bromination of the o- or p-nitrotoluene at the
temperature of about 120°-180° C., with or without carriers of halogen, there is
obtained, as already mentioned, a mixture of o- or p- nitrobenzyl chloride or bromide
and unchanged o- or p-nitrotoluene on chlorinating or brominating for instance up to
50 per cent., that is to say a molecular mixture of o- or p-nitrobenzyl chloride or
bromide, and o- or p-nitrotoluene.
If an excess of aniline or its homologues (about 2 molecules to 1 molecule of the
existing nitrobenzyl chloride) is allowed to act on this mixture under heat, a reaction
takes place, expressed by the following equation :-
The hydrochloride of aniline is removed by extracting the residue with water,
whereupon the unchanged nitrotoluene is obtained in a pure state by distilling the
residue with steam. The nitrobenzylaniline, which, as has been found, is not volatile in
vapour, remains behind and can at once be employed for manufacturing nitrobenzal-
dehyde. The process is carried out in the following manner :-
A spacious boiler-like vessel of copper or cast iron, provided with a rapidly working
agitator and means for distillation and for heating with steam, is filled with 300 kilos.
of an o- or p-nitrotoluene chlorinated up to 50 per cent. corresponding to about 170 kilos.
of o- or p-nitrobenzyl chloride and 190 kilos, of aniline or the equivalent quantity
of toluidine or xylidine or a mixture of these bases. The mixture is heated to 85° to
90° C., whereupon combination takes place according to the equation given above,
manifesting itself by the rapid rising of the temperature of the mixture to from
120° 1800 C. (according to the choice of the aniline base). As soon as the highest
temperature is reached and the thermometer begins to fall, the reaction is completed.
The mixture is allowed to cool down to about 90° C., 300 litres of water are added and
the whole is boiled, whereupon the formed hydrochloride of aniline dissolves' and may
be drawn off.
The insoluble residue, consisting of nitrobenzylaniline and nitrotoluene is distilled
.with steam, when the nitrotoluene distills over in a pure state and serves for a new
chlorination. The nitrobenzyl aniline remains behind and can be purified, if need be,
by crystallisation from alcohol or dissolving in dilute acids and by re-precipitation.
In the above example,
1. For the nitrobenzyl chlorides may be substituted the equivalent quantity of the
corresponding nitrobenzyl-bromide.
2. For the aniline or its homologues may be substituted to a certain extent, that is
to say, one half fixed alkali, alkali carbonate or acetate, alkaline earth or ammonia, in
which case an addition of 50 to 100 litres of water is advisable.
Dated this 5th day of October 1896.
ABEL & IMRAY,
Agents for the Applicant.

page_text: Manufacture of Ortho- and Para-nitrobenzyl-aniline and its
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
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 researches of Wachendorff, Haeusermann and Beck, Loesner and
others, the corresponding nitrobenzyl chloride or nitrobenzyl-bromide of the general
formula C.H
NX
, (where X represents the halogen atom,) is obtained by the
action of Chlorine or bromine, with or without application of the so called "carriers
of halogen" upon o- or p-nitrotoluene at a high temperature. A quantitative
chlorination or bromination of the two nitro-toluenes into nitrobenzyl chloride or
bromide is however not possible in this way, as a prolonged action of the halogen
produces partly ring-substitution-compounds and partly products of condensation of
complicated composition, besides the desired nitrobenzyl chloride or bromide.
With an appropriate choice of working condition 50 per cent. and more of the
nitrotoluene employed may be transformed into the corresponding nitrobenzyl baloid,
without producing any considerable quantity of the said by-product.
The close relationship between the o- and p- nitrobenzyl haloids and the chemistry
of indigo and triphenylmethane dyestuffs having become known by the fundamental
researches of A. Baeyer and F. & O. Fischer, colour manufactures soon entered this
promising field, and attempts have not been wanting, within the last 10 years, to
arrive at the separation of the pure nitrobenzyl haloid from the said raw chlorination
or bromination products.
A satisfactory solution of this problem is still unknown.
By the action of aniline or its homologues upon the nitrobenzyl haloids, the
nitrobenzyl bases of the general formula: CH, NH - CH,C,H,NO, are
obtained.
My foreign correspondents having found that the nitrobenzyl bases can easily be
transformed by oxidation into the corresponding nitro-benzylidene compounds of the
general formula: C,H, N = CH - CH, NO2, which latter compounds are split
up by diluted mineral acids into amido bases and nitrobenzaldehyde, the problem of
separating the pure nitro-benzylchloride from the above mentioned raw chlorination
or bromination product began to be of renewed interest for them.
They succeeded in carrying out this separation in a practicable manner by indirect
means, namely, by obtaining the pure nitro-benzyl bases from the raw chlorination
or bromination products of the two nitrotoluenes.
The invention may be characterized in the following way:-
By means of incomplete chlorination or bromination of the o- or p- nitrotoluene at
the temperature of about 120°-180° C., with or without carriers of halogen, there is
obtained, as already mentioned, a mixture of o- or p- nitrobenzyl chloride or bromide
and unchanged o- or p- nitrotoluene on chlorinating or brominating for instance up
to 50 per cent., that is to say a molecular mixture of o- or p- nitrobenzyl chloride or
bromide, and o- or p-nitrotoluene.
If an excess of aniline or its homologues (about 2 molecules to 1 molecule of the

page_text: existing nitrobenzyl chloride) is allowed to act on this mixture under heat, a reaction
takes place, expressed by the following equation:
that is, there is obtained a mixture of hydrochloride of aniline, nitrobenzyl-aniline
and unchanged nitrotoluene. The hydrochloride of aniline is removed by extracting
the residue with water, whereupon the nnchanged nitro toluene is obtained in a pure
state by distilling the residue with steam. The nitrobenzylaniline, which, as has
been found, is not volatile in vapour, remains behind and can at once be employed
for manufacturing nitrobenzaldehyde. The process is carried out in the following
manner
A spacious boiler-like vessel of copper or cast iron, provided with a rapidly working
agitator and means for distillation and for heating with steam, is filled with
300 kilos. of an o- or p- nitrotoluene chlorinated up to 50 per cent. corresponding to
about 170 kilos. of o- or p- nitrobenzylchloride and 190 kilos. of aniline or the
equivalent quantity of toluidine or xylidine or a mixture of these bases. The mixture
is heated to 85° to 90° C., whereupon combination takes place according to the
equation given above, manifesting itself by the rapid rising of the temperature of
the mixture to from 120°-180° C. (according to the choice of the aniline base). As
soon as the highest temperature is reached and the thermometer begins to fall, the
reaction is completed. The mixture is allowed to cool down to about 90° C.,
300 litres of water are added and the whole is boiled, whereupon the formed
hydrochloride of aniline dissolves and may be drawn off.
The insoluble residue, consisting of nitrobenzylaniline and nitrotoluene is distilled
with steam, when the nitrotoluene distills over in a pure state and serves r a new
chlorination. The nitrobenzylaniline remains behind and can be purified, if need be,
by crystallisation from alcohol or dissolving in dilute acids and by re-precipitation.
In the above example,
(1) for the nitrobenzyl chlorides may be substituted the equivalent quar ity of the
corresponding nitrobenzyl-bromide,
(2) for the aniline or its homologues may be substituted to a certain extent, that
is to say, one half fixed alkali, alkali carbonate or acetate, alkaline earth, o ammonia,
in which case an addition of 50 to 100 litres of water is advisable.
Having now particularly described and ascertained the nature of this
invention and in what manner the same is to be performed I declare hat what I
claim is:-
The herein described manufacture of o- nitrobenzyl-aniline and p-nitrobenzyl-aniline
or their homologues by heating either
(a) the mixture of o- nitrobe zylchloride or bromide and o- nitrotoluol as
obtained by incomplete chlorination or bromination of o- nitrotoluol at a high
temperature with or without application of carriers of halogen, or
(6) the mixture of p-nitrobenzylchloride or bromide and p- nitrotoluol as obtained
by incomplete chlorination or bromination of p- nitrotoluol at a high tempera-
ture with or without application of carriers of halogen with aniline or its
homologues with or without addition of fixed alkali, alkali carbonates, or
acetates, alkaline earths; or ammonia and water, and decomposing the mixture

page_text: of hydrochloride of aniline or its homologues, nitrobenzyl base and nitrotoluol
thus obtained into its components by extracting with water and distilling
with steam.