The Manufacture or Production of Ethers of Sulphuric Acid..
Year: 1893

page_text: Date of Application, 13th Jan., 1893
Complete Specification Left, 10th Oct., 1893-Accepted, 11th Nov., 1893
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICHI
BAYER & Co., of Elberfeld, in the Empire of Germany.] .
The Manufacture or Production of Ethers of Sulphuric Acid..
I HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane in the County of London, Patent Agent, do hereby declare the
nature of this invention to be as follows:-
Orlowsky describes in the "Berichte der Deutschen Chemischen Gesellschaft,"
Volume VIII (1875), page 332, that he has obtained sulphuric acid diphenolether
of the formula
are gradually added thereto, the mixture being well agitated the while. Stirring
is then continued for some time, and the heavy oil is separated from. the salt liquor.
The oil is washed with diluted soda lye, and is distilled over with steam. A clear
limpid liquor, with strong refraction, is thus produced, which boils at 200 degrees
centigrade, becoming thereby somewhat decomposed.
The isoeugenol ethyl sulphuric ether, produced in an analogous manner, boils at
248 degrees centigrade, and forms white needles, melting at 63 degrees centigrade
when crystallised from solvents.
In a similar manner, analogous mixed sulphuric ethers are obtained, for instance,

page_text: if, in place of guajacol employed in the preceding example, similar phenol-like
products are used, such as phenol, cresol, creosol, eugenol, isoeugenol, naphthol, the
analogues or homologues, or substitution products of all these components, or if the
ethyl sulphuric acid chloride above mentioned is replaced by methylsulphuric acid
chloride, butylsulphuric acid chloride, amyl sulphuric acid chloride, or analogous
sulphuric acid' chlorides.
The process of producing these new mixed sulphuric ethers of course is not
restricted to the manner explained in the foregoing example.. The mode, of
working described therein can be varied. Such modifications easily follow from
the above example, and do not alter the nature of this invention.
These mixed sulphur ethers are of special value, as they can be employed in
medicine. My foreign correspondents have discovered that these products exert,
first, a peripheric action, producing, as effect, local anesthesia, and a stronger
injection of the animal canals (stimulation of mucous membrane), and, in second
place, they exert a central action, consisting in lowering the excitement of the
central nervous system (sedative action).
The substances herein before defined accordingly possess properties which are
materially different from those of guajacol, cresols, or the like, and which consists
in a combination of central and peripheric action, the union of which has hitherto
not become known in any substance.
Dated this 12th day of January 1893.
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Manufacture or Production of Ethers of Sulphuric Acid.
I, HENRY EDWARD NEWTON of The Office for Patents, 6 Dream's Buildings,
Chancery Lane in the County of Londou, Patent Agent, do hereby declare the
nature of this invention and in what manuer the same is to be performed, to be
particularly described and ascertained in and by the following statement :-
According to Orlowsky (Berichte der Deutschen Chemischen Gesellschaft,
Volume VIII (1875) page 332), a sulphuric diphenolether, or diphenylsulphate,
of the formula SO,(OCH), is obtained by the interaction of phenol and
chlorsulphonic acid, CISO,OH.
This sulphuric diphenolether is a thick, dark coloured oil, which is decomposed
by water.
My foreign correspondents have now found, that by substituting in such sulphuric
diphenolethers, an alcohol radicle, such as methyl, ethyl, propyl, butyl, and the
like, for one of the phenolic radicles, substances are obtained which are not
decomposed when mixed with water, and which can even be distilled with steam,
possessing a powerful physiological or medical action.
My foreign correspondents prepare these new products by means of alkyl-
sulphuric chlorides, viz., by allowing the latter to act on phenols in the presence of
alkalies.
In order to illustrate this process, the following example is given; the parts
being he waicht

page_text: being well agitated the while and during some time afterwards. The resulting
heavy oil is separated from the salt liquor, washed with diluted soda Iye, and
distilled over with steam. A clear, limpid, refractive liquid is thus obtained,
which boils at 200 degrees centigrade, becoming thereby somewhat decomposed.
It is represented by the formula:
•
CHO SO, OCH ОCH
Analagous mixed sulphuric ethers are obtained in a similar manner if, in place of
the guajacol employed in the preceding example, similar phenolic products are
used, such as phenol, cresol, creosol, resorcinol, eugenol, isoeugenol, thymol,
naphthol, the analogues or homologues, or substitution products, of all these com-
ponents (such as resorcinolmonomethylether, hydroquinonemonomethylether, acetyl-
paraamidophenol, orthonitrophenol, salicylic acid, cresotinic acid, salicylic amide,
or the like, dihydroxysulphobenzide,), or if the ethylsulphuric acid chloride above
mentioned is replaced by methylsulphuric chloride, butylsulphuric chloride, amyl-
sulphuric chloride, or analogous sulphuric chlorides.
The process of producing these new mixed sulphuric ethers need not be carried
out in the precise manner explained in the foregoing example, the mode of working
described therein being merely typical, but can varied in well understood ways,
and without altering the nature of this invention.
My foreign correspondents have prepared, for instance, the following mixed
sulphuric ethers possessing the properties hereinafter mentioned.
Eugenolethylsulphuric ether (eugenolethylsulphate) obtained from eugenol and
ethylsulphuric chloride,
UgȚU DU, UU A, VUI
is a clear yellowish oil, which boils at 218 degrees centigrade, and volatilises with

page_text: C₂HO SO, OCIH NH COCH,
prepared from acetylparamidophenol and ethylsulphuric chloride, separates from
solutions thereof in diluted alcohol, in white scales which melt at 136 degrees
centigrade. It dissolves with difficulty in water and ether.
Orthonitrophenolethylsulphuric ether, prepared from ethylsulphuric chloride and
orthonitrophenol,
CH₂O SO, OCH,(CH)ОCH,,
is a highly refractive oil boiling at 225 degrees centigrade.
Guajacol-isobutylsulphuric ether, prepared from guajacol and isobutylsulphuric.
chloride,
CH,O SO, OCH OCH,
is a liquid which boils at 210 degrees centigrade, being, however, partially
decomposed at this temperature.
Guajacol-isoamylsulphuric ether, from guajacol and isoamylsulphuric chloride,
CHO SO, OCH ОCH,
is a liquid which boils at 230 degrees centigrade, but is partially decomposed at
this temperature.
This invention, however, is not restricted to the production of the afore
mentioned mixed ethers, which are merely quoted as typical examples, as other
analogous or homologous mixed sulphuric ethers can be prepared in the manner
hereinbefore defined.
These mixed sulphuric ethers are of special value, as they can be used in
medicine. My foreign correspondents have discovered that they exert, in the first
place, a peripheric action, producing local anesthesia and distension of the blood
vessels (stimulation of mucous membrane), and, in the second place, a central

page_text: action, manifested by a lessened excitability of the central nervous system (sedative
action).
The substances herein before defined accordingly possess properties which are
materially different from those of guajacol, cresols, or the like, and which consist
in a combination of central and peripheric actions,-properties which have hitherto
not been known to occur united in any one substance.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed (as communicated to me
from abroad), I declare that what I claim is :-
1. The production of mixed sulphuric ethers containing one fatty alkyl radicle
and one aromatic alkyl radicle, which process consists in allowing fatty alkyl-
sulphuric chlorides (the chlorides of fatty alkylsulphuric acids) to act on phenol
or analogous, homologous, or other phenol-like products in the presence of
alkalies.
2. The process of producing guajacolethylsulphuric ether, eugenolethylsulphuric
ether, isoeugenolethylsulphuric ether, creosolethylsulphuric ether, methylresorcinal-
ethylsulphuric ether, methylhydroquinoneethylsulphuric ether, acetyl-paraamido-
phenol ethylsulphuric ether, orthonitrophenolethylsulphuric ether, salicylic amido
ethyl sulphuric ether, and salicylic acid diethyldisulphuric ether, which process
consists in acting with ethyl sulphuric chloride on either guajacol or eugenol,
isoeugenol, creosol, the monomethylether of resorcinol, the monomethylether of
hydroquinone, acetyl-paraamido phenol, ortho nitro phenol, the amide of salicylic
acid, or salicylic acid,-the said hydroxy compounds being employed in alkaline
solution, or in the presence of alkalies.
3. The process of producing guajacolmethylsulphuric ether and creosolmethyl
sulphuric ether, by acting with methylsulphuric chloride on either guajacol or
creosol in alkaline solution, or in the presence of alkalies.
4. The process of producing guajacol, isobutylsulphuric ether, which consists in
acting with isobutylsulphuric chloride on guajacol in alkaline solution, or in the
presence of alkalies.
5. The process of producing guajacolisoamylsulphuric ether by allowing
isoamylsulphuric chloride to act on guajacol in alkaline solution, or in the presence
of alkalies.
.
6. As new products of manufacture, the mixed sulphuric ethers having the
chemical and therapeutic properties hereinbefore mentioned, and obtainable by
means of the processes defined in the foregoing Claims 1, 2, 3, 4 and 5, or by any
other process affording the same result.
7. The employment of the mixed sulphuric ethers herein before defined for
medical purposes.
Dated this 9th day of October 1893.
NEWTON & SON,
Agents for the Applicant.