The Manufacture and Production of Certain Organic Sulphates and Substances Derived Therefrom.
Year: 1898

page_text: Date of Application, 80th Deo., 1898
Complete Specification Left, 21st Sept., 1899-Accepted, 30th Mar., 1900
The Manufacture and Production of Certain Organic Sulphates and
Substances Derived Therefrom.
I, ALBERT VERLEY, of 7, Quai de Seine, Courbevoie, near Paris, in the Republic
of France, Electrician, do hereby declare the nature of this invention to be as
follows
-
My invention consists in the manufacture and production of certain organic sulphates
and substances derived therefiom. According to this invention I sulphonate bodies
containing a phenolic, or even an alcoholic, group in such a way that the sulphuric
acid group enters the phenolic, or alcoholic, group. The results which this method
of preparation gives are particularly interesting in connection with the group of
bodies employed in the manufacture of vanillin (i.e. eugenol and 150-eugenol) and
of vanillin itself but it is by no means confined to them, bemg of general
application.
I dissolve, in bisulphide of carbon, or some other neutral solvent, two moleculai
proportions of pyridine and I add thereto one molecular proportion of chloro-sulphuric
acid; keeping the mixture cool during the reaction. Chloro-sulphate of pyridine 18
formed. I then add one molecular proportion of a phenol, or of an alcohol, and the
chloro-sulphate of pyridine acts on the phenolic, or alcoholic, group, giving rise to
hydrochloric acid, which combines with the second molecule of pyridine and forms
the corresponding phenol-, or alcohol-, sulphate of pyridine.
The reaction. which gives rise to this product, is the following:-
R. OH Cl. SO,. O1. Py + Py
F
R.O. SO, OH. Pу + Py HCI.
When the reaction is finished the bisulphide of carbon is driven off on the water
bath and there remains a mixture of the two salts of pyridine. This mixture is treated
with a solution of potash until it becomes alkaline and the pyridine is driven off by
a jet of steam and recovered.
The potassium-salt thus obtained may be crystallized by evaporating to dryness and
crystallizing in water, or in alcohol. To obtain the free organic sulphate the
potassium-salt is treated, to saturation, with sulphuric, or hydrochloric, acid.
As an example of the uses to which this process can be put I will take the case of
eugenol, 180-eugenol, and vanillin.
The sulphate of eugenol prepared by the above process has the following

page_text: It is boiled with a 10 per cent. solution of potash and, after a time, becomes tians-
formed into the corresponding derivative of 180-eugenol. This is then oxidized by
some suitable oxidiser, preferably ozone, electrolysis can be used for this purpose
because the substance is soluble in water and can be treated either in an acid, or an
alkaline, solution.
In this way I obtain the sulphate corresponding to vanıllım thus :—
On heating, the vanillin separates out.
The process offers great advantages in the preparation of vanillin because the
derivative of 180-eugenol is soluble in water. The yield is very high.
The foregoing 19 given only as an example as the invention can be applied, in an
analogous manner, to other bodies of similar constitution.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
The Manufacture and Production of Certain Organic Sulphates and
Substances Derived Therefrom.
I, ALBERT VERLEY, of 7, Quai de Seine, Courbevoie, near Paris, in the Republic
of France, Electrician, 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 consists in the manufacture and production of certain organic
sulphates and substances derived therefrom.
According to this invention I sulphonate bodies containing a phenolic, or even an
alcoholic, group in such a way that the sulphuric acid group enters the phenolic, or
alcoholic group. The results which this method of preparation gives are particularly
interesting in connection with the group of bodies employed in the manufacture of
vanillin (.e. eugenol and iso-eugenol) and of vanillin itself, but it is by no meaus
confined to them, being of general application.
I dissolve, in bisulphide of carbon, or some other neutral solvent, two molecular
proportions of pyridine and I add thereto one molecular proportion of chloro-sulphurio
acid; keeping the mixture cool during the reaction. Chloro-sulphate of pyridine is
formed. I then add one molecular proportion of a phenol, or of an alcohol, and the
chloro-sulphate of pyudine acts on the phenolic, or alcoholic, group, giving rise to
hydrochloric acid, which combines with the second molecule of pyridine and forms
the corresponding phenol, or alcohol, sulphate of pyridine.
The reaction which gives use to this product, is the following

page_text: bath and there remains a mixture of the two salts of pyridine. This mixture is
treated with a solution of potash until it becomes alkaline and the pyridine 18 driven
off by a jet of steam and recovered.
The potassium salt thus obtained may by crystallized by evaporating to dryness
and crystallizing in water, or in alcohol. To obtain the free organic sulphate the
potassium salt is treated to saturation, with sulphuric, or hydrochloric acid
As an example of the uses to which this process can be put I will take the case of
eugenol, 180-eugenol, and vanillin, from which the application of the invention
generally will also be understood.
FIRST OPERATION.
Preparation of potassium eugenol sulphate 31.6 kilograms of pyridine are
dissolved in 200 kilos of bisulphide of carbon and to the liquid when cooled and
agitated 23-2 kilograms of chloro-sulphonic acid are slowly added. 35 kilos. of oil of
cloves are then poured in, and the bisulphide of carbon 18 all distilled off. The
reaction between the chloro-sulphonic acid and the pyridine, results in the formation
of pyridine chloro-sulphonate which then acts on the eugenol forming pyridine
eugenol sulphate, and liberating hydrochloric acid, according to the equation:-

page_text: Another remarkable property of potassium eugenol sulphate is the great ease
with which it is converted into potassium 180-eugenol-sulphate under the influence
of alkalis.
The presence of sulphuric acid in the eugenol molecule imparts to it a great
tendency to undergo isomerisation, and it is sufficient to boil the eugenol-sulphate 5
with 10 per cent. of potash at the ordinary pressure in order to complete the
transformation, in about two hours, according to the following equation:-
Potassium 180-eugenol sulphate is very sparingly soluble in cold water, but
dissolves readily in hot water. It melts and decomposes at 223° Centigrade.
I take advantage of the insolubility of this salt in water to completely remove
the excess of potash which has brought about the isomerisation. It suffices to
exhaust it in order to obtain it in the purified state, and the potash may be set
aside for a fresh operation, thus effecting a considerable economy. Or to obtain
180-eugenol thei so-eugenol sulphate can be decomposed at 100° Centigrade in acid
solution setting free the iso-eugenol
No trace of resin 18 produced, and the liquid remains perfectly clear and even
decolorised. The end of the reaction is readily ascertained by taking a small quantity
of the warm liquid and cooling it. While any iso-eugenol remains, a deposit of the
insoluble salt is formed on cooling, and when all the 180-eugenol 18 transformed into 30
vanillin, the liquid remains clear on cooling, because potassium vanillin sulphate is
soluble in cold water. When the reaction is completed the oxidation is interrupted
the liquid cooled, and rendered strongly acid with sulphuric acid.

page_text: at 100° Centigrade, vanillin separating as an oil which sinks to the bottom of the
liquid. The reaction is as follows:-
DisDipuate
The vanillin is sufficiently pure to be crystallized without previous conversion into
the bisulphite compound, but in order to avoid the disagreeable odour of a small
quantity of some sulphur compound which accompanies it, it is better to prepare
the bisulphite compound by the ordinary method, with a view to complete
purification.
The final yield obtained in these operations is very high almost 50 kilos. of vanillin
for 100 kilos. of eugenol.
The aforesaid chloro-sulphonic acid is preferably prepared as follows —
Sulphuric anhydride, either pure, or mixed with common acid, is saturated with
hydrogen chloride and then distilled in a glass vessel. Pure chloro sulphonic acid,
boiling at 165° Centigrade is thus obtained in one operation.
If desired soda may be used instead of potash in the treatment of the sulphate of
eugenol or the like to convert it into the corresponding iso-compound.
Having now particularly described and ascertained the nature of my inven-
tion and in what manner the same is to be performed I declare that what I
claim is
1. The manufacture of organic sulphates by sulphonating bodies containing a
phenolic group in such a way that the sulphuric acid group enters the phenolic group
substantially as hereinbefore described.
2 The manufacture of organic sulphates by sulphonating bodies containing an
alcoholic group in such a way that the sulphuric acid group enters the alcoholic group
substantially as herein before described.
3. The manufacture of phenol sulphate of pyridine by causing pyridine and chloro-
sulphuric acid to react in a neutral solvent and then adding a phenol substantially as
herein before described.
4. The manufacture of alcohol sulphate of pyridine by causing pyridine and chloro-
sulphuric acid to react in a neutral solution and then adding an alcohol substantially
as hereinbefore described.
5. The manufacture of organic sulphates by causing pyridine and chloro-sulphuric
acid to react in a neutral solvent and adding a phenol then removing the
solvent and treating the resulting mixture with potash driving off the pyridine
and saturating the potassium salt obtained with an acid substantially as hereinbefore
described.
6. The manufacture of organic sulphates by causing pyridine and chloro-sulphuric
acid to react in a neutral solvent and adding an alcohol, then removing the solvent
and treating the resulting mixture with potash, driving off the pyridine and
saturating the potassium salt obtained with an acid substantially as hereinbefore
described.
7. The manufacture of derivatives of organic sulphates by causing pyridine and
chloro-sulphuric acid to react in a neutral solvent, and adding a phenol, then removing
the solvent and treating the resulting mixture with potash driving off the pyridine,
boiling the sulphate obtained with an alkaline solution and then oxidizing the
product substantially as herein before described,

page_text: 8. In the manufacture of vanillin the production of potassium eugenol sulphate by
causing pyridine and chloro-sulphuric acid to react as a neutral solvent and adding
the phenol, then removing the solvent and treating the resulting mixture with
potash and driving off the pyridine substantially as hereinbefore described.
9. In the manufacture of vanillin the production of potassium iso-eugenol sulphate
by causing pyridine and chloro-sulphuric acid to react in a neutral solvent and adding
the phenol then removing the solvent and treating the resulting mixture with potash,
driving off the pyridine and boiling the sulphate obtained with an alkaline solution
substantially as herein before described.
10. The manufacture of iso-eugenol by causing pyridine and chloro-sulphuric acid
to react in a neutral solvent and adding the phenol then removing the solvent and
treating the resulting mixture with potash, driving off the pyridine and boiling the
sulphate obtained with an alkaline solution and thus obtaining potassium iso-eugenol
Pulphate and then decomposing this at 100° Centigrade in acid solution and thus
producing the iso-eugenol.
11. The manufacture of vanillin by causing pyridine and chloro-sulphuric acid to
react, in a neutral solvent and adding the phenol, then removing the solvent and
treating the resulting mixture with potash, driving off the pyridine, boiling the
sulphate obtained with an alkaline solution and then oxidising the product sub-
stantially as herein before described.
Dated him 07.
1000
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.