Improvements in and relating to Odourless and Tasteless Sulphur Compounds of Mineral Oils and similar Hydrocarbons.
Year: 1899

page_text: Date of Application, 1st May, 1899
Complete Specification Left, 30th Jan., 1900-Accepted, 3rd Mar., 1900
Improvements in and relating to Odourless and Tasteless Sulphur
Compounds of Mineral Oils and similar Hydrocarbons.
I, Dr. LUDWIG UTTO HELMERS, of 174, Fuhlsbüttelerstrasse, Hamburg, in the
Empire of Germany, Chemist, do hereby declare the nature of this invention
to be as follows:
:
My invention relates to the production of odourless and tasteless sulphur
compounds, obtained by the action of sulphuric acid or its substitutes on mineral
or similar oils containing sulphur in the form of sulphide.
When sulphur compounds of this class, such as thiol, petrosulphol, ichthyol,
which are produced by the action of sulphuric acid on mineral oils or similar
hydrocarbons, are treated with formaldehyde in a watery solution at ordinary
temperature, even when left standing for many days, no action takes place and
the solutions remain perfectly clear; they smell distinctly of formaldehyde and
the original substances can be precipitated by means of alkali salts.
These conditions however alter when heating for a considerable time is
resoried to. By heating a watery solution of sulphonic acid or an acidulated
solution of one of the above named salts with formaldehyde for several hours
at 100° there is gradually formed a pasty precipitation. By heating
the salts in a neutral or alkaline solution no precipitation takes place. But
there is an exception in this regard with ammoniacal salt, as in consequence
of the reaction of the formaldehyde on the ammonia the reaction soon becomes
Sour, whereupon the freed sulpho acids react with the excess of formaldehyde.
Instead of heating the dilute watery solution of the initial substances and
formaldehyde in a vessel, the reaction products of the formaldehyde may be
obtained by directly evaporating the liquids and then extracting the residue
with water; the re-action product which, however, in this case is difficult to
clean remains undissolved in the evaporating pan.
The new substances obtained by either one of the methods by treatment with
formaldehyde forms at first a pasty mass which during the washing with water.
soon assumes a more solid form and which can be dried at 1000 Centigrade without
melting. The substance so obtained forms a dark powder which is odourless
and tasteless, insoluble in water and in acids and only slowly decomposed by
alkalies.
By their behaviour towards alkalies they distinctly show their difference
not only from the initial substances which latter completely dissolve in
water as is well known, but also from the albumine (British Patent
No. 11,344 of May 6th 1897) and from the glutine-(gelatine) combinations
of ichthyol and the like, which latter, although insoluble in water and in acids,
can be easily dissolved in alkalies while splitting up into their components.
This also explains the advantage obtained in therapeutics from the use of these
new preparations. Consequent on their being difficult to dissolve in alkaline
liquids the reaction products of the formaldehyde with the preparations com-

page_text: bined with sulphur in the form of sulphide when taken for internal use, become
only slowly absorbed and they thus exercise a weak but long enduring effect.
T
فضل
سلاكسيمل
1800
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C.,
Agents for the Applicant.
Improvements in and relating to Odourless and Tasteless Sulphur
Compounds of Mineral Oils and similar Hydrocarbons.
1, Dr. Ludwig OTTO HELMERS, of 174, Fuhlsbüttelerstrasse, 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; —
My invention relates to the production of odourless and tasteless sulphur
compounds, obtained by the action of sulphuric acid or its substitutes on mineral
or similar oils containing sulphur.
When sulphur compounds of this class, such as thiol, petrosulfol, ichthyol,
which are produced by the action of sulphuric acid on mineral oils or similar
hydrocarbons, are treated with formaldehyde in a watery solution at ordinary
temperature, even if left standing for many days, no action takes place, and
the solutions remain perfectly clear: they smell distinctly of formaldehyde, and
the original substances can be precipitated by means of alkaline salts.
These conditions however after when heating for a considerable time is
resorted to. By heating a watery solution of sulphuric acid, or an acidulated
solution of one of the above named salts with formaldehyde for several hours
at 100° Centigrade, there is gradually formed a pasty precipitate. By heating
the salts in a neutral or alkaline solution no precipitation takes place. There
is an exception however in this respect with regard to ammoniacal salt, in con-
sequence of the reaction of the formaldehyde on the ammonia, the reaction
products soon becomes sour, whereupon the freed sulpho acids react with the
excess of formaldehyde.
Instead of heating the dilute watery solution of the initial substances and
formaldehyde, the reaction products of the formaldehyde may be obtained by
directly evaporating the liquids, and then extracting the residue with water;
the reaction product which, however, in this case is difficult to clean, remains
undissolved in the evaporating pan.
The new substances obtained by either one of the methods by treatment with
formaldehyde, forms at first a pasty mass, which, during the washing with water,
soon assumes a more solid form and can be dried at 100° Centigrade without
melting. The substance so obtained forms a dark powder which is odourless
and tasteless, insoluble in water and acids and is only slowly decomposed by
alkalies.
By the behaviour of the said substance towards alkalies it exhibits a distinct
difference, not only from the original substances, which latter completely dis-
solve in water as is well known, but also from albumine-British Patent
No. 11,344 dated May 6th 1897) and from the glutine-(gelatine) combinations
of ichthyol and the like, which latter, although insoluble in water and in acids.
can be easily dissolved in alkalies while splitting up into their components.
This also, explains the advantage obtained in therapeutics from the use of these
new preparations. Consequent on their being difficult to dissolve in alkaline

page_text: liquids, the reaction products of the formaldehyde with the preparations com-
bined with sulphur in the form of sulphide when taken for internal use, become
only slowly assimilated by the system and thus exercise a weak but long
enduring effect.
The following method of preparing my improved sulphur compounds may be
given as an example:-
-
2 kilos. of a 25% watery solution of ichthyol sulpho acid are mixed with
about kilo. formaline, containing 40% per cent. of formaldehyde.
This
mixture is then heated for 10 hours over a water bath. After cooling, the
liquid is drawn off from the precipitate, which is then repeatedly washed with
water, and finally dried at 100° Centigrade.
Having now particularly described and ascertained the nature of my said
invention and in what manner the same is to be performed, 1 declare that what
I claim is
1. The process of producing odourless and tasteless preparations from sul-
phonized compounds derived from sulphureted mineral oils and similar hydro-
carbons by treatment with sulphuric acid. which consists in heating an acid or
ammoniacal solution of the said sulphonized compounds with formaldehyde,
substantially as set forth.
2. As a new product of manufacture the hereindescribed preparation con-
sisting of formaldehyde and a sulphonized compound derived from sulphureted
hydrocarbons, which preparation is of greenish brown colour, contains sulphur,
is soluble in water and acids and free from odour and smell.
HASELTINE, LAKE & Co.,
45. Southampton Buildings, London, W.C.,
Agents for the Applicant.