Improvements in the Process of Obtaining Aqueous Solutions of Phenols and other Substances.
Year: 1893

page_text: Date of Application, 26th Oct., 1893
Complete Specification Left, 28th June, 1894-Accepted, 4th Aug., 1894
PROVISIONAL SPECIFICATION.
Improvements in the Process of Obtaining Aqueous Solutions of
Phenols and other Substances.
I, Dr. LUDWIG OTTO HELMERS, of 21 Bohnenstrasse, Hamburg, in the
Empire of Germany, Chemist, do hereby declare the nature of this invention to be
as follows:-
Numerous attempts have of late been made to render the homologues of carbolic
acid easily soluble in water by the addition of indifferent substances and thereby
better utilize the disinfecting power of phenols, and increase the disinfecting
property of the same.
In making an investigation respecting products which are formed in the treatment
of mineral oils with sulphuric acid I found a series of new solvents for phenols.
It is known that by the action of sulphuric acid under suitable conditions
upon many mineral oils, resin oils and other hydrocarbons, substances of a nature
similar to the sulpho acids of tumenol (Letters Patent No. 19502 A.D. 1890),
ichthyol, thiol, thiolinic acid and the like are obtained, which by themselves or
in the form of their salts are soluble in water. If the components soluble in
alcohol are withdrawn from these neutral or neutralized substances by extraction,
a residue remains behind which is insoluble in water, but which by the addition
of the alcoholic extract becomes again soluble in water. Accordingly the original
product which is soluble in water contains substances which are insoluble in water
and which can be obtained in an aqueous solution only by the presence of a
substance soluble by itself in water and at the same time also soluble in alcohol.
I was led to infer from this that the said component which may be withdrawn
by alcohol from the neutral mixture and which I will briefly term "anytin,"
would impart also to other than the above-mentioned substances insoluble in water
the property of dissolving in water, and trials made in that respect have in many
cases confirmed this inference. For the sake of simplicity all such preparations,
namely mixtures of a substance which is by itself insoluble in water, with anytin,
which mixtures are soluble in water, I will call "anytols."
Such anytols may in most cases be manufactured by simply mixing an anytin
with the substances to be rendered soluble in water, only in some instances it is
better to mix the alcoholic solutions of the ingredients and then distil off again the
alcohol.
Before dealing more particularly with the substances capable of being thus
rendered soluble in water by means of anytin it may be observed that the power
of anytin to effect the transformation from insolubility to solubility in water or
what I will hereinafter call its "transforming power" depends on the nature of the
hydrocarbons treated with sulphuric acid and on the conditions prevailing during
the reaction. There exists therefore a whole series of anytins. The original
product soluble in water possesses a slight but still clearly perceptible transforming
power in respect of many substances insoluble in water. This property is doubtless
caused by the considerable quantity of anytin contained in the crude product, and
the transforming power of which is however already reduced to some extent by the
The concentrated aqueous
admixture of compounds which are insoluble in water.
mixtures of these crude anytins with the substances to be transformed often
separate part of the water when standing, but when an ample quantity of water is
added a homogeneous mixing takes place.
Instead of preparing the anytins proper by extraction with alcohol 1 may
prepare them from the crude anytins by treating the same with a dissolving agent

page_text: which does not attack the anytins but dissolves only the admixed substances con-
taining sulphur which are insoluble in water. Solvents of this kind are ether,
benzol, chloroform and others.
Of the compounds which in the presence of anytins dissolve in water, the
phenols are the most important. A mixture of equal parts of cresol and an
anytin, which was prepared from a mineral oil rich in sulphur, formed a clear
solution with water which could be diluted to any desired extent. Guaiacol,
creosote, thymol and the like, and also mixtures of the same with each other and
with phenols boiling at higher temperatures, behave similarly to cresol. Moreover,
in an aqueous solution many hydrocarbons are transformed by anytin, such as
benzol and its homologues, terpenes and some mineral oils, also ethereal oils and
camphors. Also the solubility in water of many other substances of quite a
different chemical character, such as iodine, nitrobenzol, aniline, is considerably
increased by the presence of anytins.
Dated this 26th day of October 1893.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C., Agents for the Applicant.
COMPLETE SPECIFICATION.
Improvements in the Process of Obtaining Aqueous Solutions of
Phenols and other Substances.
I, Dr. LUDWIG OTTO HELMERS, of 21 Bohnenstrasse, Hamburg, 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:-
Numerous attempts have been made to render the homologues of carbolic acid
easily soluble in water by the addition of indifferent substances and thereby better
utilize the disinfecting power of phenols, and increases the disinfecting property of
the same.
In making an investigation respecting products which are formed in the treatment
of mineral oils with sulphuric acid I found a series of new solvents for phenols.
It is known that by the action of sulphuric acid under suitable conditions upon
the sulphuretted or non-saturated constituents of mineral and similar oils-for
instance the Seefeld mineral oils, the artificially sulphuretted oil described in the
Specification of the German Patent No. 38416, the non-saturated hydrocarbons
mentioned in the Specification of the British Patent No. 19502 A.D. 1890, sulpho-
nized carbon compounds of a nature similar to ichthyol, thiol, tumenol and like
substances are obtained, which by themselves or in the form of their alkali salts
are soluble in water.
As set forth in the Specification of my British Patent No. 6044 A.D 1893 these
sulphonized carbon compounds consist of two different substances of which the one
(sulphonic acid salt) is per se soluble in water, while the other (sulphone like body)
is per se insoluble in water. The separation is to be performed either by extracting.
the former with alcohol (ethylic or other alcohols), or by extracting the latter
with benzol (CH) or the like. In the said Specification I have further mentioned
that the sulphone like bodies obtained in this manner become again soluble in
water by mixing them with the sulphonic acid salts, i.e. with the constituents, per se
oluble in water, of the neutralized reaction product obtained by treating mineral
or similar oils with concentrated sulphuric acid or its substitutes. Therefore,
the presence of these sulphonic acid salts effects that the sulphone like bodies,
per se insoluble in water, dissolve in water, and I was led to conclude from this
that the said sulphonic acid salts would also impart to other substances insoluble
in water the property of dissolving in water.

page_text: Trials made in that respect shewed that a great series of substances insoluble or
insufficiently soluble in water become soluble in water in any proportion by mixing
these substances with the sulphonic acid salts above mentioned. In those cases,
in which it is desired to render soluble solid substances it will be requisite to
dissolve in alcohol both the sulphonic acid salts and the substances to be made
soluble in water, then to mix the alcoholic solutions and to distil off the alcohol
afterwards.
Among the substances which in this manner have been made soluble in water in
any proportions the phenols are the most characteristic ones: cresol, guaiacol.
thymol and the like and also mixtures of the same with each other and with other
phenols of a higher boiling point form a clear solution with water, when mixed with
the sulphonic acid salts. Moreover, many hydrocarbons, such as benzol and its
homologues, terpenes, and some mineral oils, also ethereal oils and camphors are
rendered clearly soluble in water when mixed with the said sulphonic acid salts..
Also the solubility in water of many other substances of quite a different chemical
character, such as iodine, nitrobenzol, aniline, is considerably increased by the
addition of the sulphonic acid salts. Therefore the applicability of a great number
of substances having therapeutical and disinfecting value is materially improved.
The quantity of the sulphonic acid salts required to render completely soluble the
substances per se insoluble or insufficiently soluble in water depends upon the nature
of these substances. For instance, cresols are rendered soluble in water by mixing
the same with an equal quantity of sulphonic acid salts, while benzol requires
nearly threefold and camphor tenfold quantity of the sulphonic acid salts.
Instead of employing the pure sulphonic acid salts the reaction mixture obtained
by treating mineral or similar oils with concentrated sulphuric acid, after being
neutralized by an alkali, may be used on account of its contents of sulphonic acid
salts to render soluble such substances which are per se insoluble or insufficiently
soluble in water. Of course, a proportionally larger quantity of this crude product
is required in the respective cases, because the dissolving power is already partly
consumed by the presence of sulphone like bodies per se insoluble in water.
Having now particularly described and ascertained the nature of my said inven--
tion, and in what manner the same is to be performed, I declare that what I
claim is:-
1. The process of rendering soluble in water phenols, hydrocarbons, ethereal
oils, camphor, iodine or other substances per se insoluble or insufficiently soluble in
water, which consists in mixing such substances with the sulphonized carbon com-
pounds or their component parts per se soluble in water produced by treating the
sulphuretted or non-saturated constituents of mineral and similar oils with sulphuric
acid or its substitutes and by neutralizing the obtained reaction mixture with an
alkali.
2. As new products of manufacture the mixtures, soluble in water, of phenols,
hydrocarbons, ethereal oils, camphor, iodine or other substances per se insoluble or
insufficiently soluble in water, with the sulphonized carbon compounds or their
component parts per se soluble in water, produced by treating the sulphuretted or
non-saturated constituents of mineral or similar oils with sulphuric acid or its
substitutes and neutralizing the so obtained reaction mixture with an alkali,
substantially as set forth.
3. The use of the herein described products defined by Claim 2 as therapeutical
and disinfecting agents.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C., Agents for the Applicant.