THE PRODUCTION OF VANILLINE FROM OIL OF CLOVES
Year: 1876

page_text: LETTERS PATENT to Dr. Ferdinand Tiemann, of Brunswick, of the Empire of
Germany, for the Invention of "THE PRODUCTION OF VANILLINE FROM OIL OF
CLOVES."
Sealed the 14th October 1876, and dated the 20th April 1876.
PROVISIONAL SPECIFICATION left by the said Ferdinand Tiemann at the
Office of the Commissioners of Patents on the 20th April 1876.
Dr. FERDINAND TIEMANN, of Brunswick, of the Empire of Germany. "THE
PRODUCTION OF VANILLINE FROM OIL OF CLOVES."
Oil of cloves consists of eugenol and an indifferent hydrocarbon.
In carrying out this Invention and to separate the two constituents one from
another the oil of cloves is diluted with three times its volume of ether. The
etheric solution is then agitated with a weak solution of hydrate of sodium or
potassium, which latter then takes all the eugenol and leaves the indifferent hydro-
carbon in the ether. After having acidulated the alkaline solution of eugenol by
means of sulphuric acid, hydrochloric acid, or the like, it is again agitated with
ether to take up all the eugenol which can then be obtained in a pure state by
distilling. Pure eugenol is heated for a couple of hours with acetic anhydride, and
thereby changed into aceto-eugenol. The cooled liquid is carefully distributed
with warm water and a solution of permanganate of potassium, the warm water
being allowed to flow gradually into it, and at the same time the liquid is stirred
constantly. By means of permanganate of potassium the aceto-eugenol is oxydized,
and the hydrate of the maganese dioxide is separated. To the liquid filtered
from the latter hydrate of sodium is added in a small excess to give it a weak
alkaline reaction when the liquid is to be evaporated to the required volume. The
liquid concentrated in this way is acidulated with sulphuric or hydrochloric acid
and agitated with ether, which last then holds the vanilline formed in the described
way, and which is purified by any one of the known methods.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed by
the said Ferdinand Tiemann in the Great Seal Patent Office on the 20th
October 1876.
Dr. FERDINAND TIEMANN, of Brunswick, of the Empire of Germany.
PRODUCTION OF VANILLINE FROM OIL OF CLOVES."
"THE
The object of this Invention is the production of vaniline from oil of cloves,
and I will premise that oil of cloves consists of eugenol and an indifferent hydro-
carbon.
In carrying out this Invention, and to separate the two constituents one from
another, the oil of cloves is diluted with three times its volume of ether. The
etheric solution is then agitated with a weak solution. of hydrate of sodium or
potassium, which latter takes up all the eugenol and leaves the indifferent hydro-
carbon in the ether. After having acidulated the alkaline solution of eugenol by
means of sulphuric acid or hydrochloric acid or the like it is again agitated with
ether to take up the eugenol, which can then be obtained in a pure state by
distilling. Pure eugenol is heated for about two hours with acetic anhydride, and
thereby changed into aceto-eugenol, and this liquid when cooled is to be carefully
diluted with about 20 litres of warm water, and then into this mixture is allowed
to flow gradually a solution of (1½ k°) of permanganate of potassium in about 200
litres of warm water, during which time. the liquid is kept constantly stirred.. By
means of permanganate of potassium the aceto-eugenol is oxydized and the hydrate
of the manganese dioxide is separated out. To the liquid filtered from the latter
hydrate of sodium is added in a small excess to give it a weak alkaline reaction
when the liquid is to be evaporated to the volume of about 25 litres. The liquid
concentrated in this way is acidulated with sulphuric or hydrochloric acid and
agitated with ether, which last then takes up the vanilline formed in the described
manner, and this is then purified by any one or other of the known methods.
Having now described the nature and particulars of my said Invention, I claim
the production of vanilline from oil of cloves, substantially as set forth.
In witness whereof, I, the said Ferdinand Tiemann, have hereunto set my hand
and seal, this Fourth day of October, in the year of our Lord One thousand
eight hundred and seventy-six.
FERD. TIEMANN. (L.S.)