Process for Production and Treatment of Oxidisable Derivates of Orthonitro-benzylchloride.
Year: 1888

page_text: Date of Application, 22nd Oct., 1888
Complete Specification Left, 11th July, 1889-Accepted, 17th Aug.,
1889
PROVISIONAL SPECIFICATION.
Process for Production and Treatment of Oxidisable Derivates of
Orthonitro-benzylchloride.
I, Dr. EUGEN FISCHER, of Schloss Strasse No. 29, Stuttgart, in the Empire of
Germany, Chemist, do hereby declare the nature of this invention to be as
follows:
Success has not hitherto attended the efforts to convert the easily obtained
Orthonitro-benzylchloride into the corresponding Nitrobenzaldehide in the same way
as has long been practised in obtaining oil of bitter almonds and Paranitro-
benzaldehide from the corresponding Benzylchlorides. If for instance the Orthonitro
benzylchloride be treated with ordinary oxidizing agents either no reaction takes
place, or the decomposition is carried too far resulting in the production of some
Orthonitrobenzoic acids, but mostly dark brown to black fatty masses.
simply boiling the chloride with water there occurs mainly a formation of black
brown fatty matters, in contradistinction to the behaviour of Paranitrobenzylchloride
which, as is well known, is easily converted into Paranitrobenzylalcohol.
But even on
It is no doubt partly owing to this fact that up to the present time there have been
no further attempts to use Orthonitrobenzylchloride for the production of Orthonitro-
benzaldehyde (see Dr. S. Friedlander, Fortschritt der Theerfarben fabrikation 1877-
1887 P 141).
Recourse was rather taken to other methods that are mostly difficult and not easily
carried out in practice in order to obtain the Orthonitrated oils of bitter almonds,
which are in many cases of importance (see Berichte d deutsch. Chem. Gesellschaft 14,
2801 and Geriman Patents Nos. 21683, 30329, 31842, 32238, 33 64).
I have found that the conversion of Orthonitrobenzylchloride into the desired
Aldehyde is effected much more readily, and generally without any material formation
of bye-products, if, in the first instance, the chlorine of the first named body is
replaced by corresponding element groups; that is to say, ethers or acid esters of
Orthonitrobenzyl are formed (in a similar manner as, for example, has been variously
carried out with Paranitrobenzyl chloride, see Zeitschrift f. Ch. 1867 p 562, Ann. Ch.
Ph. Vol 217 p 214, Ann Ch. Ph Vol 224 p 104 and following, Ber der Deutsch Chem.
Ges. Vol 2 p 238 &c.) and the bodies obtained in this way are subjected in a suitable
manner to the action of oxidizing agents.
It is also advantageous to obtain from these bodies by saponification Orthonitro-
benzylalcohol, which is then converted in the known way into Aldehyde.
I have found Orthonitrobenzylacetate to be particularly suitable for the above
purpose, but other derivatives of the same class may also be used as suitable for
oxidation, as compared with the original chloride, such as Orthonitrobenzyl sulphurous
acid, and the salts thereof, Orthonitrobenzylbenzoate, Orthonitrobenzylethyl ether &c.
For the preparation of these bodies I will give the following examples
:-
1
1. 100 parts of Orthonitrobenzyl chloride are boiled during from 70 to 8 hour's,
together with 360 parts of alcohol, and 60 to 70 parts of dehydrated acetate of soda,
in an apparatus with reflux cooler; the solution is then separated from the precipitated
Na Cl, the spirit is distilled off, and the residue is stirred up with a small quantity of
cold water, whereby the Orthonitrobenzyl acetate is obtained as a white crystalline
mass. This contains a small quantity of Orthonitrobenzylalcohol and traces of
Orthonitrobenzylethyle-ether. The acetate is readily soluble in alcohol, ether, and hot
or (less readily) cold benzole. From the last named solvent it crystallizes in fine
white. needles having a melting point: of 71° C. (uncorrected) which become first

page_text: reddish and then of quite a dark colour in the air. In this example the sodium
acetate can be replaced by other acetates and the alcohol by other solvents such as
glacial acetic acid, wood spirit &c.
The duration of the boiling can be shortened by the use of a greater quantity of
acetate, or by raising the boiling temperature.
11. 100 parts of Orthonitrobenzyl chloride, 350 parts of spirits and 100 to 120 parts
of potassium benzoate are heated at the reflux cooler, and the process is otherwise
carried out in a similar manner to that described under I. The Orthonitrobenzyl
benzoate crystallizes out of hot alcohol, in which it is tolerably soluble, in yellow
crystals, very much interwoven, having a melting point of 94° ((uncorrected). In
cold alcohol it dissolves with difficulty.
III. 100 parts of Orthonitrobenzyl chloride are heated to from 70° to 80° C.
together with from 80 to 100 parts of neutral sodium sulphite or a corresponding
quantity of another sulphite, and from 300 to 400 parts of water, during from 12
to 14 hours until all the chloride has disappeared. From the light yellow solution
the Orthonitrobenzyl sulphite of soda crystallizes in glassy flat spikes, or also in
greyish white scales. An addition of Na Cl increases the separation.
From hot alcohol the salt crystallizes in small lustrous needles grouped
concentrically.
IV. 100 parts of Orthonitrobenzyl chloride are dissolved in about 330 parts of
alcohol and are heated at the reflux cooler under addition of about 60 parts of sulpho-
cyanide of potassium.
The mass remains at first, without additional external heating, in slight ebullition,
with strong separation of K Ci.
After boiling for several hours, the K C is separated and the alcohol is driven off,
whereupon the residue solidifies in crystals on the addition of water. The Ortho-
nitrobenzyl rhodanide crystallizes out of alcohol in slightly yellow tablets having a
melting point of 68° C.
The Orthonitrobenzaldehyde I then obtain direct from the above bodies, for example
in the following manner :-
V. 100 parts of Orthonitrobenzyl acetate is boiled with 250 parts of lead superoxide
paste of 513 p. c. Pb O, and 250 parts of water. After 6 hours I add slowly 150 parts
acetic acid of 40 p. c. CH, O, after further 3 hours boiling this is filtered.
On cooling, Orthonitrobenzaldehyde separates from the solution first in an oily and
then in crystalline form.
This is purified by known methods. Orthonitrobenzoic acid is not formed at all in
this way, or at least only in small quantity. The lead superoxide can be replaced by
corresponding quantities of other oxidizing agents, such as Mn U₂ (K₂ Cr₂ 07) &c.
Instead of acetic acid other acids may also be used with more or less advantage.
Good results are also obtained by the following method:-
VI. 100 parts of Orthonitrobenzylacetate are dissolved at ordinary temperature in
70 parts of sulphuric acid of about 60°. The temperature is then raised to from 35°
to 40° C. and from 30.5 to 31 parts of nitric acid of 70° H NO,, or equivalent
quantities of a nitrate are added slowly under continual stirring, whereby after a
certain time nitric oxide gas will escape in a steady stream. The temperature is best 4
maintained at from 37° to 38° C.
After the whole of the oxidizing agent has been introduced, the mass is kept warm
until the evolution of gas ceases, and lastly the previously cooled solution is poured
into about 2400 parts of cold water.
After standing for several hours the Orthonitrobenzaldehyde which has formed into 5
light yellow needles, is separated by filtration.
This is almost chemically pure, if the process has been carried out correctly. The
small quantities of Aldehyde that have remained in solution are separated in the
known manner from the dilute sulphuric acid.
In place of the Orthonitrobenzyl acetate, other Nitrobenzyl-ethers or esters may be 5
used with more or less advantage.

page_text: VII. If instead of producing the Aldehyde directly from the ethers, or esters, it is
desired to first produce the corresponding alcohol from these, and then to convert the
alcohol according to known methods into Aldehyde (a method which is particularly
advantageous on account of the possibility of regaining the sodium acetate employed)
the mode of proceeding is as follows:-
The spirit solution separated from the Na Cl according to example I is gradually
mixed with aqueous alkaline lye, under stirring and keeping at low temperature, until
the liquid, which at first has a rapid neutral reaction, remains slightly alkaline, even
after long standing.
For example 58 parts of soda lye of 40 p. c. Na OH are added by degrees. After
about one third of the base has been added, a crystalline separation takes place, which
eventually forms the entire liquid into a magna. After 24 hours the spirit is distilled
off, any excess of alkali that may be present being previously neutralized. To the
residue of distillation is added the necessary quantity of water for dissolving the
sodium acetate, whereby the Orthonitrobenzyl alcohol remains as a white crystalline
mass.
1 11
33
1
1
ABEL & IMRAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Process for Production and Treatment of Oxidisable Derivates of
Orthonitro-benzylchloride.
I, Dr. EUGEN FISCHER, of Schloss Strasse No. 29, Stuttgart, in the Empire of
Germany, Chemist, 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 :-
Success has not hitherto attended the efforts to convert the easily obtained Ortho-
nitro-benzylchloride into the corresponding Nitrobenzaldehide in the same way as has
long been practised in obtaining oil of bitter almonds and Paranitrobenzaldehide from
the corresponding Benzylchlorides. If for instance the Orthonitro-benzylchloride be
treated with ordinary oxidizing agents, either no reaction takes place, or the decom-
position is carried too far, resulting in the production of some Orthonitro-benzoic
acids, but mostly dark brown to black fatty masses. But even on simply boiling the
chloride with water there occurs mainly a formation of black-brown fatty matters, in
contra-distinction to the behaviour of Paranitrobenzylchloride which, as is well known,
is easily converted into Paranitrobenzylalcohol.
It is no doubt parily owing to this fact that up to the present time there have been
no further attempts to use Orthonitrobenzylchloride for the production of Orthonitro-
benzaldehyde (see Dr. S. Friedlander Fortschritt der Theerfarbenfabrik-action 1877-
1887 P. 141).
Recourse was rather taken to other methods that are mostly difficult and not easily
carried out in practice for obtaining this body.
I have found that the conversion of Orthonitro-benzylchloride into the desired
aldehyde is effected generally without any material formation of bye products if, in
the first instance, ethers or acid ethers of orthonitrobenzylic alcohol- are formed by
treating the orthonitrobenzylchloride with alchohols or with the salts of some organic
or inorganic acids and the bodies obtained in this way are subjected in a suitable
manner to the action of oxidizing agents.
I have found orthonitrobenzylacetate to be particularly suitable for the above
purpose, but other derivatives of the same class may also be used such as orthonitro-
benzylethyle ether, orthonitrobenzylthiosulphuric acid and the salts thereof, ortho-
nitrobenzylbenzoate, orthonitrobenzyloxalate, formiate &c.
These bodies are then treated with the well known oxidizing agents, like peroxyde
of lead peroxyde of manganese, Chromic acid, nitric acid &c.

page_text: They may also be converted by saponification into the orthonitrobenzylic alcohol or
the latter may be prepared by treating the orthonitrobenzylamine with nitrous acid
and the orthonitrobenzylic alcohol, thus obtained is then oxydised in a suitable
manner.
For the preparation of ethers and acid ethers of orthonitrobenzylic alcohol, I will
give the following examples.
I. 100 parts of orthonitrobenzyl chloride are boiled during from 70 to 80 hours,
together with 360 parts of alcohol, and 60 to 70 parts of dehydrated acetate of soda,
in an apparatus with reflux cooler; the solution is then separated from the precipitated
chloride of sodium, the spirit is distilled off, and the residue is stirred up with a small
quantity of cold water, whereby the orthonitrobenzyl acetate is obtained as a white
crystalline mass. This contains a small quantity of orthonitrobenzylalcohol and traces
of Orthonitrobenzylethyle ether. The acetate is readily soluble in alcohol, ether, and
hot or (less readily) cold benzole. From the last named solvent it crystallizes in fine
white needles which become first reddish and then of quite a dark colour in the air.
In this example the sodium acetate can be replaced by other acetates and the alcohol
by other solvents such as glacial acetic acid, wood spirit &c.
The duration of the boiling can be shortened by the use of a greater quantity of
acetate, or by raising the boiling temperature.
II. 100 parts of orthonitrobenzyl chloride 350 parts of spirits and 100 to 120 parts
of potassium-benzoate are heated in the reflux cooler, and the process is otherwise
carried out in a similar manner to that described under L.
The orthonitrobenzylbenzoate crystallizes out of hot alcohol, in which it is tolerably
soluble, in yellow crystals, very much interwoven having a melting point of 94° C.
In cold alcohol it dissolves with difficulty.
III. 100 parts of orthonitrobenzylchloride are heated to from 50° to 60° C. together
with about 200 parts of hyposulphite of soda and 100 parts of water during from 12
to 14 hours until all the chloride has disappeared. After several hours the ortho-
nitrobenzylthiosulphonate of soda crystallises from the solution in brilliant white
scales. An addition of common salt increases the separation. From hot alcohol the
salt crystallizes in small lustrous needles.
IV. 100 parts of orthonitrobenzylacetate is boiled with 250 parts of lead superoxide
paste of 513 p. c. Pb O, and 250 parts of water. After 6 hours there are added
slowly 150 parts acetic acid of 40 p. c. C₂ H₁ O₂; after further several hours boiling
this is filtered.
On cooling, Orthonitrobenzaldehyde separates from the solution first in an oily and
then in crystalline form. This is purified by known methods. Orthonitrobenzoic
acid is not formed at all in this way, or at least only in small quantity. The lead
superoxide can be replaced by corresponding quantities of other oxidizing agents,
such as Mn O, K, Cr, O, &c.
Instead of acetic acid, other acids, may also be used with more or less advantage.
Good results are also obtained by the following method:
V. 100 parts of orthonitrobenzylacetate are dissolved at ordinary temperature in
700 parts of sulphuric acid of about 60°. The temperature is then raised to from 35°
to 40° C. and from 30.5 to 31 parts of nitric acid of 70 p. c. H NO,, or equivalent
quantities of a nitrate are added slowly under continual stirring, whereby, after a
certain time nitric oxide gas will escape in a steady stream. The temperature is best
maintained at from 37° to 35° C.
After the whole of the oxidizing agent has been introduced, the mass is kept warm
until the evolution of gas ceases, and lastly the previously cooled solution is poured
into about 2,400 parts of cold water.
After standing for several hours the Orthonitrobenzaldehyde which has formed into
light yellow needles, is separated by filtration.
This is almost chemically pure, if the process has been carried out correctly. The
small quantities of aldehyde that have remained in solution are separated in the known
manner from the dilute sulphuric acid.

page_text: In place of the orthonitrobenzyl acetate, other Nitrobenzylethers or esters may be
used with more or less advantage.
VI. If instead of producing the aldebyde directly from the ethers or esters it is
desired to first produce the corresponding alcohol from these, and then to convert the
alcohol according to known methods into aldehyde (a method which is particularly
advantageous on account of the possibility of regaining the sodium acetate employed)
the mode of proceeding is as follows:
The spirit solution separated from the Na Cl according to example I is gradually
mixed with aqueous alkaline lye under stirring and keeping at low temperature until
the liquid which at first has a rapid neutral reaction, remains slightly alkaline, even
after long standing.
For example, 58 parts of soda lye of 40 p. c. Na OH are added by degrees. After
about one third of the base has been added a crystalline separation takes place which
eventually forms the entire liquid into a magma. After 24 hours the spirit is
distilled off, any excess of alkali that may be present being previously neutralized.
To the residue of distillation is added the necessary quantity of water for dissolving
the sodium acetate whereby the orthonitrobenzylalcohol remains as a white crystalline
mass.
Having thus described the nature of my invention and the manner of performing
the
same, I would have it understood that 1 do not confine myself to the exact details
of the process herein before given; but what I claim is
The production of orthonitrobenzaldehyde by means of orthonitrobenzylchloride,
substantially as herein before described.
ABEL & IMRAY,
Agents for the Applicant.