provements in the Manufacture of Oxidation Products of Nitro- toluene
Year: 1899

page_text: Date of Application, 4th Nov., 1899
Complete Specification Left, 4th Aug., 1900--Accepted, 22nd Sept., 1900
66
PROVISIONAL SPECIFICATION
Improvements in the Manufacture of Oxidation Products of Nitro-
toluene "
I, JAMES YALE Jonsson of 47 Lancolns Tun Fields in the County of London,
Gentleman do hereby declare the nature of this invention (which has been com-
municated to me from abroad by the Badische Anilin & Soda Fabiik of Ludwig-
hafen-on-Rhine in the German Empire) to be as follows
It is known that certam methyl derivatives of benzene can be oxidised in
he side chain by means of manganese perexide in acid solution and so converted
into coresponding aldehyde compounds, see the Specification of the German
Patent No 101,221 According to the said specification the formation of
carboxylic acid is almost entirely prevented when a large excess of the methyl
derivative is present during the reaction the although toluene, xylene,
and the hike are readily oxidized, the oxidation of ortho nitto toluene proceeds
with difficulty under the conditions theicin descubed Thus if ortho-nitro-toluene
be treated according to the conditions described in the examples on and two of the
and specification that is to say, at a temperature of forty degrees, on twenty hve
degrees Centigrade respectively at the very highest, traces of ortho-mitio benzal-
dehyde e formed
My feign corespondents have found that under suitable conditions herem-
after set forth the oxidation of ortho-nitro-toluene in the side cham can be very
teadily effected with the und of manganese peroxide and sulphuric acid It the
conditions be suitably chosen ortho nilio benzaldehyd, or the conesponding
earboxyhe acid can be obtamed as desired, even though an excess of ortho nitro-
toluene be present
The conditions to be observed are that the temperature must
be essentially higher over one hundred degrees Centigrade and the concentration
of the sulphuric acid must be varied according to the object it is desired to effect.
It dilute acid be used ortho nitio-benzaldehyd is the product obtained whilst
with stronger acids ortho-mitio-benzoic acul is the principal product It is
ecommended that the treatment be eftected in closed vessels, so that the mass
can be heated above the boiling point under ordinary pressure and the desued
temperature of reaction obtained When working with stronger acids an
aangement should be made to neutralize the effect of the water formed diluting
the sulphuric acid, namely, by adding, during the reaction, more concentrated
cid The vessel in which the reaction is effected is preferably lined with lead
aud furnished with a stue and a manometer, and it should be provided with
a valve which, whilst mamtaming the desned pressure, permits the escape of
the reaction gases if the pressure ses higher than is desirable
The following examples will serve to illustrate the nature of the invention,
but the invention is not confined to the examples. The parts are by weight:

page_text: Mix together one hundred parts of ortho-nitro-toluene, one thousand patts
of dilute sulphuc acid (containing from thnty-five to forty-eight po cent
HS) and two hundred parts of finely powdered manganese peroxide. Intio-
duce the mixture into a vessel capable of withstanding pressure, arranged as
herein before stated and heat for about two, or three, hos at a temperature of
about one hundred and fifty five degrees to one hundred and sixty five degrees Cen-
tigrade Adjust the valve of the vessel so that a pressure of about ten atmospheres
is not exceeded When the reaction is finished allow the mixture to stand so
that any manganese peroxide in suspension may settle Collect the oil which
floats upon the acid liquid and wash it with water and with a solution of
carbonate of ɛo'la This treatment withdiaws any ortho-nitro-benzoic acid that
may have been formed as a bye-product Shake the oil after this treatment
with sodium bisulphite in the cold The ortho-nitio-benzaldehyd dissolves and
Pan be separated, and obtained in a nearly pure condition, by the addition of
alkahes
EXAMPLE II
PRODUCTION OF ORTHO-NITRO BENZOIC ACID AS MAIN-PRODUCT.
Prepare a mixture of the same ingredients as those set forth m Example I,
except that stronger acul is to be taken, namely acid containing from sixty two
to seventy eight per cent of H₂SO, Heat the mixture in the pressure vessels
preferably only to a temperature of one hundred and thuty five to one hundred
and forty five degrees Centigrade Adjust the safety valve so that the gas
formed during the reaction con escape if the pressure rises too high When
working in this way, on treating the oil that results in the manner described m
Example 1 a large quantity of ortho-nitro-benzoic acid is obtained a small
quentity of catho-nitio-benzaldehyd being mixed with it a bye-product It is
not absolutely necessary to work in closed vessels under pressure Simila result,
can be obtained when working at ordinary temperature using a vessel provided
with an inverted condenser, but when working in this way concentrated sulphu
od is added, during the reaction, to maintain the strength of the acid in spite
of the formation of water during the reaction
Dated this 4th day of November 1899
JOHNSONS & WILLCOX,
47 Lincolns Inn Fields London W C
Agents
66
COMPLETE SPECIFICATION (AMENDED)
Improvements in the Manufacture of Oxidation Products of Nitro-
toluene "
I JAMES YAIT JOHNSON of 47 Lincolns Inn Fields in the County of London,
Gentleman do hereby declare the nature of this invention (which has been com-
municated to me from abroad by the Badische Anilin & Soda Fabrik of Ludwig-
hoten-on-Rhine in the German Impue) and in what manner the same is to be
performed to be particularly described and ascertained in and by the following
statement.
It is known that certain methyl denvatives of benzene ein be oxidized in

page_text: the side cham by means of manganese peroxide in acid solution and so converted
into conesponding aldehyde compounds, see the Specification of the German
Patent No 101221, and also the Specification of British Letters Patent No 22121
of 1897 According to the said specifications the formation of carboxylic acid
is almost entirely prevented when a leige excess of the methyl derivative is
present during the ieaction
My foreign correspondents have ascertained that by using a temperature of
not less than 100° C they can dispense with any excess of ortho-nitio-toluene
at all stages of and at the end of the re-action If the conditions be suitably
chosen ortho-nitro-benzaldehyde, on the conesponding carboxylic veid, can be
obtamed, as desired The conditions to be observed are that the temperature
must be ovel one hundred degrees Centigrade, and the concentration of the
sulphure acid must be varied according to the object it is desued to effect If
dilute acid be used ortho-nitro-benzaldehyde is the product obtained: whilst,
with stronger acids, ortho-nitio-benzoic acid is the principal product It is
1ecommended that the treatment be effected in closed vessels, so that the mass
can be heated above the boiling point under ordinary pressure and the desired
temperature of reaction obtamed When working with stronger acids aange
ments should be made to add during the reaction, more concentrated acid in
order to neutralise the effect of the water formed diluting the sulphuric acid
The vessel in which the reaction is effected is preferably lined with lead, and
furnished with a stuer and a manometer, and it should be provided with a
valve which, whilst maintaining the desued pressure, permits the escape of the
I caction ୧୦୨୧୪ if the pressure ise higher than is desnable
The following examples will serve to further illustrate the nature of the
invention and the manner in which it can be carried into practical effect but the
14
1
L
Mix together one hundred parts of ortho-nitro-toluene, one thousand parts
of dilute sulphuric acid (contaming from thuty-five, to forty-eight, por cent
ISO) and two hundred parts of finely powdered manganese peroxide. Intro-
duce the mixture into a vessel capable of withstanding the requisite pressure
and aanged as herembefore stated, and heat for about two, on three, hours at
a temperature of about one hundred and forty degies to one hundred and
sixty-five degrees Centigrade Adjust the valve of the vessel so that a pressute
of about ten atmospheres is not exceeded When the reaction is finished allow
the mixture to stand so that any manganese peroxide in suspension may settle
Collect the oil which floats upon the acid liquid and wash it with water and
with a solution of carbonate of soda This treatment withdiaws any ortho-
mtio-benzone acid that may have been formed as a bye-product. Shake the oil,
after this treatment, with sodium bisulphite in the cold The ortho-nitio-
benzaldehyde dissolves and can be separated, and obtained in a nearly pure
condition, by the addition of alkalies
EXAMPLE
PRODUCTION OF ORTHO-NITRO-BENZOIC ACID AS MAIN PROLUCI
Prepare a mixture of the same ingredients as those set forth in the foregoing
Example 1, except that stronger acid is to be taken, namely, acid containing from
sixty-two to seventy-eight per cent of H₂SO, Heat the mixture in the pressure
vessels, preferably only to a temperature of one hundred and thirty-five, to
one hundred and forty-five degrees Centigrade. Adjust the safety valve so
that the gas formed duing the caction can escape if the pressure rise too high
When working in this way, on treating the oil that results in the manuer

page_text: described in the foregoing Example 1, a laige quantity of ortho-nitio-benzoic
acid is obtained a small quantity of ortho-nitio-benzaldehyde being mixed with
it as a bye-product It is not absolutely necessary to work in closed vessels
under pressure. Similar results can be obtamed when working at ordinary
pressure using a vessel provided with an inverted condenser, but when working
in this was concentrated sulphuric acid is added, during the reaction, to maintai
the strength of the acid in spite of the formation of water during the reaction
Having now particularly descubed and ascertamed the nature of this inven
tion and in what manner the same is to be performed I declare that what I
claim 18:
1 The oxidation of ortho-nitio-toluene with manganese peroxide and sulphune
acid of the concentrations helenbefore set forth at a temperature over one
hundred degrees Centigrade
The manufacture of ortho-nitio-benzaldehyde as main product and ortho-
nitio-benzoic acid as bye-product by treating under pressure ortho-nitro-toluene
with manganese peroxide and dilute sulphuric acid, containing from thuty-hve
to forty-eight per cent H₂SO, at a temperature higher than one hundred degrees
Centigiade, substantially as herembefore described
The manufacture of ortho-nitio-benzoic acid as main product and ortho-
nitio-benzaldehyde 83 by product by treating ortho-nitro-toluene with
manganese peroxide and sulphuric acid containing from sixty-two to seventy-
eight per cent HO, at a temperature above one hundred degrees Centigrade.
substantially as hereinbefore described
4 The oxidation of ortho-nitio-toluene substantially as described in the
foregoing examples respectively
Dated this 4th day of August 1900
JOHNSONS & WILLCOX,
47 Lincoln's Inn Fields, London, W.C.
Agents