Improvements in the Manufactures of Mixtures of Ortho- Chlor- and Ortho Nitro-benzylalcohol, or Mixtures of the Ethers of these Two Substituted Alcohols, and the Separation of such Mixtures.
Year: 1898

page_text: Date of Application, 17th May, 1898
Complete Specification Left, 17th Feb., 1899-Accepted, 25th Mar.,
1899
Improvements in the Manufactures of Mixtures of Ortho- Chlor- and
Ortho Nitro-benzylalcohol, or Mixtures of the Ethers of these
Two Substituted Alcohols, and the Separation of such Mixtures.
I, GEORGE WILLIAM JOHNSON, of 47, Lincoln's Inn Fields, in the County of
London, Patent Agent, do hereby declare the nature of this invention (which has
been communicated to me from abroad by Kalle & Co., of Biebrich-on-Rhine, in
the Empire of Germany), to be as follows:-
-
When acting upon ortho-nitrotoluol with chlorine at elevated temperatures (from
120° to 180° Centigrade for example), in the presence or not, of bodies able to
expedite the chlorinating process mainly two benzylchloride derivatives are formed,
namely ortho-nitro-benzylchloride and ortho-chlor-benzyl-chloride. Whilst the
former is a normal substitution product of the ortho-nitrotoluol employed, for the
formation of the latter not only had the methyl group of the starting material to
be chlorinated but the nitro-group had to be eliminated and replaced by chlorine.
It is advisable to proceed with the chlorination only so far that about half of the
quantity of nitrotoluol employed is attacked by the chlorine. In this manner
principally ortho nitro-benzylchloride is formed.
It is possible to separate the chlorinated products formed by this reaction from
each other and from the nitrotoluol, but such separation is rather difficult and
causes great loss of material.
My foreign correspondents have found that the benzylchloride-derivatives con-
tained in the crude chlorination-product can easily be transformed into the corre-
sponding substituted benzyl-ethers and benzyl-alcohols and that these bodies can,
without difficulty be separated from each other and from the unchanged ortho-
nitrotoluol. The ethers as well as the alcohols can easily be transformed into the
corresponding ortho-substituted aldehydes, which are very valuable. Since the
ortho-chlor and the ortho-nitrobenzaldehyde can easily be separated from each
other, a previous separation of the ortho-chlor from the ortho-nitro-benzyl ethers,
or of the ortho-chlor- from the ortho-nitro-benzyl alcohol, is not necessary before
working them up for the aldehydes.
If the crude chlorinated oil, after having been freed from acid by washing with
feebly alkaline water, be boiled with salts of certain organic or inorganic acids
with the addition of water or spirits, the corresponding ortho-nitro- and ortho-chlor-
benzyl ethers are formed. As examples of organic and inorganic acids the salts
of which are suitable for this purpose I name the following: Acetic acid, oxalic
acid, benzoic acid, phtalic acid, thiosulphuric (hyposulphurous) acid, and thiocyanic
(hydrorhodanic) acid.
These acids yield according to their special chemical nature, the neutral ethers
insoluble in water or the salts of the corresponding acid ethers soluble in water.
The separation of the ethers from the nitrotoluol can be effected in various
manners. If ethers are formed which are soluble in water the nitrotoluol is drawn
off from the aqueous liquid, from which the ethers are precipitated by adding

page_text: common salt. In the case of ethers insoluble in water the alcohol used in their
preparation is distilled off, and then the nitrotoluol is driven over with steam.
Some ortho-chlorbenzylethers are to a certain degree volatile with steam, but much
less than ortho-nitrotoiuol, so that also these ethers can be isolated by distilling the
nitrotoluol over with steam, if the distillation be carefully conducted. In both cases
the ethers are obtained after cooling in solid form. They are filtered and pressed.
For the transformation into the alcohols the mixture of the two ethers is treated
with an alcoholic solution of a caustic alkali at ordinary temperature or boiled
with an aqueous solution of an alkali carbonate. The two alcohols are obtained in
solid form and are separated from each other by distillation with steam: the ortho-
chlorbenzyl alcohol is easily driven over by steam whilst the ortho nitrobenzyl
alcohol is scarcely volatile.
The saponification of the ortho-chlor and ortho nitro-benzylthioethers leads to
the formation of thio-alcohols, or sulphides. For the preparation of the alcohols
it is not necessary to previously separate the ethers from the nitrotoluol. The
formation of the ethers, and of the alcohols may be effected in one operation and
in this manner the alcohols may be produced directly from the crude chlorinated
oil. For this purpose the crude chlorinated oil, freed from acid by washing is
boiled in alcoholic solution with an aqueous solution of a salt, such for instance as
sodium acetate and sodium carbonate, until the intermediately formed ethers are
completely saponified. The alcohol is now distilled off and then the ortho nitro-
toluol and the ortho-chlorbenzylalcohol are driven over with steam. The ortho-
nitrobenzyl alcohol remains as an oil which becomes solid on cooling, and may
be purified by filtering and pressing. From the distillate, especially from the last
fractions, the ortho-chlorbenzylalcohol crystallises out. It is filtered off the ortho-
nitrotoluol and may be purified by crystallization from water. It crystallizes from
aqueous solutions in white needles, which melt at 720 Centigrade.
For this method of producing the mixture of the benzyl alcohol derivatives the
presence of a salt, such as sodium acetate is necessary, because the ethers have to
be formed intermediately in order to obtain a good result.
The ortho-chlor and the ortho-nitro-benzyl-alcohol may be separated from the
nitrotoluol in the following manner. The mixture, obtained after forming the
ethers, saponifying them, and distilling off the alcohol, is extracted by means of
sulphuric acid of about 60° Bé., which dissolves the two substituted benzylalcohols
and scarcely acts at all upon the orthonitrotoluol. The solution so obtained of the
ortho-chlor and the ortho-nitrobenzylalcohol in sulphuric acid is drawn off from
the unchanged nitrotoluol and can be worked up directly for the corresponding
benzaldehyde derivatives.
11
11
1
1000
JOHNSONS & WILLCOX.
47, Lincoln's Inn Fields, London, W.C.,
Agents.
Improvements in the Manufacture of Mixtures of Ortho- Chlor- and
Ortho Nitro-benzylalcohol, or Mixtures of the Ethers of these 4
Two Substituted Alcohols, and the Separation of such Mixtures.
I. GEORGE WILLIAM JOHNSON, of 47, Lincoln's Inn Fields, in the County of
London, Patent Agent, do hereby declare the nature of this invention (which has
been communicated to me from abroad by Kalle & Co., of Biebrich-on-Rhine, in

page_text: the German Empire), and in what manner the same is to be performed to be
particularly described and ascertained in and by the following statement:-
When acting upon ortho nitro-toluol with chlorine at elevated temperatures
(from 120° to 180° Centigrade for example) in the presence or not, of bodies which
will expedite the chlorinating process, mainly two benzylchloride derivatives are
formed, namely ortho-nitro-benzylchloride and ortho-chlor-benzylchloride. Whilst
the former is a normal substitution product of the ortho- nitrotoluol employed, for
the formation of the latter, not only had the methyl group of the starting material
to be chlorinated but the nitro-group had to be eliminated and replaced by chlorine.
It is advisable to proceed with the chlorination only so far that about Falf of the
quantity of nitro-toluol employed is attacked by the chlorine. In this manner
principally ortho-nitro-benzylchloride is formed." It is possible to separate the
chlorinated products, formed by this reaction, from each other and from the nitro-
toluol; but such separation is rather difficult and causes great loss of material.
My foreign correspondents have found that the benzylchloride-derivatives, con-
tained in the crude, chlorination-product, can easily be transformed into the corre-
sponding substituted benzyl-ethers and benzyl-alcohols and that these bodies can,
without difficulty be separated from each other and from the unchanged ortho-
nitro-toluol. The ethers, as well as the alcohols, can easily be transformed into the
corresponding ortho-substituted aldehydes, which are very valuable.
If the crude chlorinated oil, after having been freed from acid by washing with
feebly alkaline water, be boiled with salts of certain organic, or inorganic, acids,
with the addition of water, or spirits, the corresponding ortho-nitro and ortho-chlor-
benzylethers are formed. As examples of organic and inorganic acids, the salts
of which are suitable for this purpose, I name the following: Acetic acid, oxalic
acid, benzoic acid, phtalic acid, thiosulphuric (hyposulphurous) acid and thiocyanic
(hydrorhodanic) acid.
These acids yield, according to their special chemical nature, the neutral ethers
insoluble in water or the salts of the corresponding acid ethers soluble in water.
The separation of the ethers from the nitro-toluol can be effected in various
manners. If ethers which are soluble in water are formed, the nitro-toluol is drawn
off from the aqueous liquid, from which the ethers are precipitated by adding
common salt. In the case of ethers insoluble in water, the alcohol used in their
preparation is distilled off, and then the nitro-toluol is driven over with steam.
Some ortho-chlor-benzylethers are, to a certain degree, volatile with steam, but
much less than ortho-nitro-toluol, so that these ethers also can be isolated by dis-
tilling the nitro-toluol over with steam, if the distillation be carefully conducted.
In both cases the ethers are obtained, after cooling, in solid form. They are
filtered and pressed.
For the transformation into the alcohols the mixture of the two ethers is treated
with an alcoholic solution of a caustic alkali at ordinary temperature, or boiled
with an aqueous solution of an alkali carbonate. The two alcoliols are obtained in
solid form and are separated from each other by distillation with steam; the
ortho-chlor-benzylalcohol is easily driven over by steam, whilst the ortho-nitro-
benzylalcohol is scarcely volatile.
The saponification of the ortho-chlor-, and ortho-nitro-, benzylthio-ethers leads
to the formation of thio-alcohols, or sulphides.
For the preparation of the alcohols it is not necessary to previously separate the
ethers from the nitro-toluol. The formation of the ethers, and of the alcohols, may
be effected in one operation, and in this manner the alcohols may be produced
directly from the crude chlorinated oil. For this purpose the crude chlorinated
oil, freed from acid by washing, is boiled in alcoholic solution with an aqueous
solution of a salt, such for instance, as sodium acetate, and sodium carbonate, until
the ethers intermediately formed are completely saponified. The alcohol is now
distilled off and then the ortho-nitro-toluol and the ortho-chlor-benzylalcohol are
driven over with steam. The ortho-nitro-benzylalcohol remains as an oil which

page_text: becomes solid on cooling, and may be purified by filtering and pressing. From the
distillate, especially from the last fractions, the ortho-chlor-benzylalcohol crystallizes
It is filtered off from the ortho-nitro-toluol and can be purified by crystalliza-
tion from water. It crystallizes from aqueous solutions in white needles, which
melt at 720 Centigrade.
out.
For this method of producing the mixture of the benzylalcohol-derivatives the
presence of a salt, such as sodium acetate, is necessary, because the ethers have to
be formed intermediately in order to obtain a good result.
Since the ortho-chlor-, and the ortho-nitro-benzaldehyde can easily be separated
from each other, a previous separation of the ortho-chlor-, from the ortho-nitro-
benzylethers, or of the ortho-chlor, from the ortho-nitro-benzylalcohol, is not neces-
sary before working them up for the aldehydes.
The ortho-chlor-, and the ortho-nitro-, benzylalcohol may be separated from the
nitro-toluol in the following manner. The mixture, obtained after forming the
ethers, saponifying them, and distilling off the alcohol, is extracted by means of
sulphuric acid, of about 60° Bé, which dissolves the two substituted benzylalcohols,
and scarcely acts at all upon the ortho-nitro-toluol. The solution so obtained of
the ortho-chlor-, and the ortho-nitro-, benzylalcohol in sulphuric acid is drawn off
from the unchanged nitro-toluol and can be worked up directly for the corresponding
benzaldehyde derivatives.
We give in the following example the manner in which the process according
to this invention can best be carried out on a manufacturing scale:
600 kilos. of chlorinated oil, containing about 40 per cent. of benzylchloride
derivatives, are boiled in a reflux cooler with 800 litres of dilute alcohol, 250 kilos.
crystallized sodium acetate and 90 kilos. of soda ash, until the intermediately
formed ortho-nitro-, and ortho-chlor- benzylacetate are saponified. The alcohol
is now distilled off. On cooling, a mixture of the corresponding substituted benzyl-
alcohols crystallizes out from the reaction mass. It is however not necessary to
wait for this. It has been found preferable to carry on the distillation, after all
the alcohol is distilled over, by passing a current of steam through the reaction
mass. This treatment is continued as long as a sample of the distillate yields, on
cooling, any considerable separation of ortho-chlor-benzylalcohol. The residue con-
tains the by-products of the chlorination and consists mainly of ortho-nitro-benzyl-
alcohol. After cooling it is filtered and pressed. For the purpose of further
purification, the ortho-nitro-benzylalcohol may be recrystallized from hot water.
The ortho-chlor-benzylalcohol crystallizes, on cooling, from the distillate, which
also contains the unchanged ortho-nitro-toluol, besides by-products of the chlorina-
tion. The ortho-chlor-benzylalcohol being much less volatile with steam than
is ortho-nitro-toluol, it is advisable, for its better isolation, to keep the first fractions
of the distillate, which contain yet very little ortho-chlor-benzylalcohol, separate
from the later ones which, on cooling, yield crystallizations of this compound.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed, I declare that what I
claim is:
1. The manufacture of a mixture of the ortho-chlor-, and of the ortho-nitro-,
benzyl ethers from chlorinated ortho-nitro-, toluol, by treating the crude chlorinated
oil, after washing it with alkaline water, with such compounds as are suitable to
transform the ortho-chlor-, and the ortho-nitro-, benzylchloride into compounds
having the nature of an ether and separating these ethers from the unchanged
ortho-nitro-toluol in the manner herein before described.
2. The manufacture of a mixture of ortho-chlor-, and ortho-nitro-, benzylalcohol
and isolating these two compounds by saponifying the mixture of the ethers,
obtained by the process claimed under the preceding claim, by means of alkaline
agents and separating the ortho-chlor-benzylalcohol from the ortho-nitro-benzyl
alcohol by distillation with steam.

page_text: 3. In the manufacture and isolation of ortho-chlor-, and ortho-nitro-, benzyl-
alcohol from chlorinated ortho-nitro-toluol by the process for the production of
the ethers claimed under the preceding first claim adding from the commencement
not only such agents, as are suitable for transforming the benzylchloride deriva-
tives into compounds having the nature of an ether, but also soda, or bodies acting
similarly, and continuing the action of these bodies on the chlorinated oil until the
intermediately formed ethers are saponified, yielding the alcohols, and distilling
the unchanged ortho-nitro-toluol and the ortho-chlor-benzylalcohol off from the
ortho-nitro-benzylalcohol by means of steam, and filtering off the ortho-chlor-
benzylalcohol crystallizing from the distillate.
Dated this 17th day of February 1899.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C.,
Agents.