Improvements in the Production of Para-nitro-phenetol, and of Homologous Ethers of Para-nitro-phenol, and of Ortho-nitro- toluene-para-sulphonic Acid.
Year: 1895

page_text: Date of Application, 17th Dec., 1895
Complete Specification Left, 17th Sept., 1896--Accepted, 31st Oct., 1896
PROVISIONAL SPECIFICATION.
Improvements in the Production of Para-nitro-phenetol, and of
Homologous Ethers of Para-nitro-phenol, and of Ortho-nitro-
toluene-para-sulphonic Acid.
A communication from abroad by LA SOCIÉTÉ CHIMIQUE DES USINES DU
RHONE, anct. GILLIARD, P. MONNET & CARTIER, of Lyons, France,
Manufacturers.
I, GEORGE BELOE ELLIS of the Firm of J. C. Mewburn & Ellis of 55
and 56 Chancery Lane in the County of London, Chartered Patent Agents, do
hereby declare the nature of this invention to be as follows:-
-
This invention has reference to the production of para-nitro-phenetol and ortho-
nitro-toluene-para-sulphonic acid.
Para-nitro-phenetol, the ethyl ether of para-nitro phenol, which enters into the
manufacture of various pharmaceutical products, has hitherto been prepared from
phenol by nitration and subsequent etherification of the paranitrophenol obtained
s one of the products of nitration by means of ethyl chloride or ethyl iodide.
Direct nitration of phenol always produces the two isomerides, ortho- and para-
nitrophenol, in proportions varying according to the conditions of nitration, and
up to the present time it has been impossible to obtain in this manner one or
the other of the isomerides exclusively, and the operation is moreover always
accompanied by the formation of tarry products which are of little or no value.
According to the present invention, phenol is combined with an aromatic sulpho-
chloride, preferably with paratoluenesulphochloride, in the presence of alkali,
whereby an ester is obtained which can easily be nitrated without production of
tarry products, and with the exclusive formation of a para-nitro-phenol derivative.
The para-toluene sulphonic ester of phenol is then nitrated and a nitro group is
thus introduced into the toluene radical in the ortho position simultaneously with
the nitration of phenol in the para-position, and the para-nitrophenol ester of ortho-
nitrotolueneparasulphonic acid is formed.
This dinitrated ester is subsequently heated on the water bath with an alcoholic
solution of sodium or potassium ethoxide, or simply with a solution of sodium or
potassium bydroxide in ethyl alcohol; it thus becomes split up, as my foreign
correspondents have discovered, into para-nitrophenetol and ortho-nitrotoluene-
parasulphonate of sodium or potassium.
The chemical reactions which take place in performing these operations may be
represented by the following equations :-

page_text: In carrying out the invention the phenol sulphonic ester can be prepared in
the usual way by dissolving sodium phenolate in five times its weight of water
at 80° C., and adding the theoretical quantity of para-toluene-sulpho-chloride,
stirring vigorously the whole time. On cooling, the ester is separated in a pure state
in theoretical quantity.
The nitration of the paratoluenesulphonic acid phenol ester can be effected by
making an intimate mixture of 100 kilos. of phenol ester of paratoluenesulphonic
acid with 100 kilos. of potassium nitrate and adding the mixture in small quantities
at a time to 1000 kilos. of sulphuric acid (66° B.), the temperature being
maintained at 15° C. throughout the operation by any suitable means of cooling
the mass.
When the reaction is finished, the nitrated product is separated from the
sulphuric acid by filtration or centrifugal action and well washed with water.
Under these conditions only the dinitrated product indicated above is formed,
namely ortho-nitro-toluene-para-sulphonic-acid-para-nitro-phenol-ester, which melts
at 115° C.
The splitting up or decomposition of the nitrated ester into para-nitrophenetol
and ortho-nitro-toluene para-sulphonic acid may be conveniently carried out in the
following manner. Two kilos. of metallic sodium are dissolved in 200 kilos.
absolute ethyl alcohol and to this solution 20 kilos. of the dinitro ester are added.
The whole is boiled for several hours on the water bath in a vessel provided with
a reflux condenser and then the excess of alcohol is distilled off. By subsequent
distillation in a current of steam, para-nitro-phenetol passes over in a pure state,
leaving in the retort a solution of ortho-nitro-toluene-parasulphonate of sodium.
From the latter, ortho-nitro-toluene-parasulphonic acid is precipitated by dilute
mineral acids; it may be employed in the manufacture of vanillin.
It is evident that by the employment of the inferior or superior homologues of
ethyl alcohol in the place of ethyl alcohol in the above process, the corresponding
ethers of para-nitro-phenol may be obtained in like manner.
Dated this 17th day of December 1895.
J. C. MEWBURN & ELLIS,
55 and 56 Chancery Lane, London, Chartered Patent Agents.
COMPLETE SPECIFICATION.
Improvements in the Production of Para-nitro-phenetol, and of
Homologous Ethers of Para-nitro-phenol, and of Ortho-nitro-
toluene-para-sulphonic Acid.
A communication from abroad by LA SOCIÉTÉ CHIMIQUE DES USINES DU
RHÔNE, auct. GILLIARD, P. MONNET & CARTIER, of Lyons, France,
.Manufacturers.
J, GEORGE BELOE ELLIS of the Firm of J. C. Mewburn & Ellis of
55 and 56 Chancery Lane in the County of London, Chartered Patent Agents,
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:-
This invention has reference to the production of para-nitro-phenetol and ortho-
nitro-toluene-para-sulphonic acid.
Para-nitro-phenetol, the ethyl ether of para-nitro-phenol which enters into the
manufacture of various pharmaceutical products, has hitherto been prepared from
phenol by nitration and subsequent etherification of the paranitrophenol obtained
as one of the products of nitration by means of ethyl chloride or ethyl iodide.

page_text: Direct nitration of phenol always produces the two isomerides, ortho- and para-
nitro-phenol, in proportions varying according to the conditions of nitration, and
up to the present time it has been impossible to obtain in this manner one or the
other of the isomerides exclusively, and the operation is moreover always
accompanied by the formation of tarry products which are of little or no value.
According to the present invention, phenol is combined with an aromatic sulpho-
chloride, preferably with paratoluenesulphochloride, in the presence of alkali,.
whereby an ester is obtained which can easily be nitrated without production of
tarry products, and with the exclusive formation of a para-nitro-phenol derivative.
The para-toluene sulphonic ester of phenol is then nitrated and a nitro group is.
thus introduced into the toluene radical in the ortho position simultaneously with
the nitration of phenol in the para-position, and the para-nitrophenol ester of
ortho-nitrotolueneparasulphonic acid is formed.
This dinitrated ester is subsequently heated on the water bath with an alcoholic
solution of sodium or potassium ethoxide, or simply with a solution of sodium or
potassium hydroxide in ethyl alcohol; it thus becomes split up, as my foreign
correspondents have discovered, into para-nitro-phenetol and ortho-nitrotoluene-
parasulphonate of sodium or potassium.
The chemical reactions which take place in performing these operations may be
represented by the following equations
3. CH3
> SO₂-0 NO₂+C2H5ONa=CH3
>SO₂ONa+ C₂H50<
>NO₂+H₂O
NO2
NO2
In carrying out the invention' the phenol sulphonic ester can be prepared in the
usual way by dissolving sodium phenolate in five times its weight of water at 80° C.,
and adding the theoretical quantity of para-toluene-sulpho chloride, stirring
vigorously the whole time. On cooling, the ester is separated in a pure state in
theoretical quantity.
The nitration of the paratoluenesulphonic acid phenol ester can be effected by
making an intimate mixture of 100 kilos. of phenol ester of paratoluene sulphonic
acid with 100 kilos. of potassium nitrate and adding the mixture in small
quantities at a time to 1000 kilos. of sulphuric acid (66° B.) the temperature being
maintained at 15° C. throughout the operation by any suitable means of cooling
the mass.
The corresponding quantity of nitric acid in concentrated solution can
be substituted for the nitrate of potassium.
When the reaction is finished, the nitrated product is separated from the
sulphuric acid by filtration or centrifugal action and well washed with water.
Under these conditions only the dinitrated product indicated above is formed
namely ortho-nitro-toluene-para-sulphonic-acid-para-nitro-phenol-ester, which after
recrystallisation from benzene melts at 115° C.
The splitting up or decomposition of the nitrated ester into para-uitrophenetol
and ortho-citro-toluene parasulphonic acid may be conveniently carried out in the
following manner. Two kilos. of metallic sodium, or the corresponding quantity
of caustic soda or potass, are dissolved in 200 kilos. absolute ethyl alcohol and to
this solution 20 kilos. of the dinitro ester are added. The whole is boiled for
several hours on the water bath in a vessel provided with a reflux condenser and
then the excess of alcohol is distilled off. By subsequent distillation in a current
of steam; para-nitro-phenetol passes over in a pure state, leaving in the retort a

page_text: solution of ortho-nitro-toluene-parasulphonate of sodium. From the latter, ortho-
nitro-toluene-para sulphonic acid is precipitated by dilute mineral acids; it may
'be employed in the manufacture of vanillin.
It is evident that by the employment of the inferior or superior homologues of
ethyl alcohol in the place of ethyl alcohol in the above process, the corresponding
ethers of para-nitro-phenol may be obtained in like manner.
In lieu of the para-toluene-sulpho-chloride in the manufacture of para-nitro-
phenetol as above described other aromatic sulpho-chlorides such as benzene-sulpho-
chloride, ortho-toluene-sulpho-chloride, alpha- or beta-naphtulene-sulpho-chloride
etc. may be employed in the same manner save that different proportions by weight
of the sulpho-chlorides and their derived compounds must be used according to their
molécular weight.
Having now particularly described and ascertained the nature of this inven-
tion as communicated to me and in what manner the same is to be performed, I
declare that what I claim is :-
1. The manufacture of paranitrophenetol or of homologous ethers of para-
nitro-phenol by the saponification with alkalies of the para-nitro-phenol ester of
ortho-nitro-toluene-para-sulphonic acid in alcoholic solution, substantially as
described.
2. The process of obtaining alkyl ethers of para-nitro-phenol by treatment of
the nitrated aromatic sulphonic esters of para-nitro-phenol with alkalies in alcoholic
solution, substantially as described.
3. The production of para-uitro-phenetol and ortho-nitro-toluene-para-sulphonic
acid simultaneously by nitration of the ester of para toluene-sulphonic acid into a
dinitrated product and its saponification in alcoholic solution, and the separation of
the two dissociation products substantially as described.
Dated this 17th day of September 1896.
J. C. MEWBURN & ELLIS,
55 and 56 Chancery Lane, London, Chartered Patent Agents.