A NEW PROCESS FOR THE ARTIFICIAL PRODUCTION OF VANILLIN BY MEANS OF CONIFERINE OR THE SAP OF PLANTS BELONGING TO THE SPECIES OF CONIFERA, OR ANY OTHER PLANTS RELATED TO THIS FAMILY, AS AN EXTRACT OF ALL THESE PAR CONTAINING CONIPER
Year: 1874

page_text: ETTERS PATENT to Wilhelm Haarmann, of 34 & 36, Georgen-
strasse, Berlin, in the Empire of Germany, Analytical Chemist,
Dr. of Philosophy, for the Invention of "A NEW PROCESS FOR THE
ARTIFICIAL PRODUCTION OF VANILLIN BY MEANS OF CONIFERINE OR THE SAP
OF PLANTS BELONGING TO THE SPECIES OF CONIFERA, OR ANY OTHER PLANTS
RELATED TO THIS FAMILY, AS AN EXTRACT OF ALL THESE PARTS OF THE JUST
MENTIONED PLANTS CONTAINING CONIPERINE."
PROVISIONAL SPECIFICATION left by the said Wilhelm Haarmann
at the Office of the Commissioners of Patents, with his Petition,
on the 25th February 1874..
I, WILHELM HAARMANN, of 34 & 36, Georgen Strasse, Berlin, in the
Empire of Germany, Analytical Chemist, Dr. of Philosophy, do hereby
declare the nature of the said Invention for "A NEW PROCESS FOR THE
ARTIFICIAL PRODUCTION OF VANILLIN BY MEANS OF CONIFERINE OR THE SAP OF
PLANTS BELONGING TO THE SPÈCIES OF CONIFERA, OR ANY OTHER PLANTS RELATED TO

page_text: THIS FAMILY, AS AN EXTRACT OF ALL THESE PARTS OF THE JUST MENTIONED PLANTS
CONTAINING CONIFERINE," to be as follows:-
Take, first, coniferine; or, secondly, the sap of the plants mentioned
above, which has been purified or liberated from albumina or other
impurities; or thirdly, an extract of all those parts of the just mentioned
plants containing coniferine; or fourthly, the products obtained from
coniferine by means of fermentation, putrefaction, or similar action, and
treat one or other with oxydizing agents or such agents of similar action,
such as bichromate of potassium and sulphuric acid, or any other
peroxide, oxide, acid, or salt which produce the same effect. The
product of the reaction in all these cases is artificial vanillin, which has
been proved to be identical in all physical and chemical properties
with the aromatic principle obtained by the extraction, etc. of the natural
vanilla beans.
SPECIFICATION in pursuance of the conditions of the Letters Patent,
filed by the said Wilhelm Haarmann in the Great Seal Patent Office
on the 22nd August 1874.
TO ALL TO WHOM THESE PRESENTS SHALL COME, WILHELM
HAARMANN, of 34 and 36, Georgen Strasse, Berlin, in the Empire of
Germany, Analytical Chemist, Doctor of Philosophy, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Twenty-fifth day of February, in the year
of our Lord One thousand eight hundred and seventy-four, in the thirty-
seventh year of Her reign, did, for Herself, Her heirs and successors,
give and grant unto me, the said Wilhelm Haarmann, Her special
licence that I, the said Wilhelm Haarmann, my executors, admini-
strators, and assigns, or such others as I, the said Wilhelm Haarmann,
my executors, administrators, and assigns, should at any time agree
with, and no others, from time to time and at all times thereafter
during the term therein expressed, should and lawfully might make,
usc, excrcise, and vend, within the United Kingdom of Great Britain
and Ireland, the Channel Islands, and Isle of Man, an Invention for
"A NEW PROCESS FOR THE ARTIFICIAL PRODUCTION OF VANILLIN BY MEANS OF

page_text: CONIFERINE OR THE SAP OF PLANTS BELONGING TO THE SPECIES OF CONIPERA, OR
ANY OTHER PLANTS RELATED TO THIS FAMILY, AS AN EXTRACT OF ALL THOSE PARTS
OF THE JUST MENTIONED PLANTS CONTAINING CONIPERINE," upon the condition
(amongst others) that I, the said Wilhelm Haarmann, my executors or
administrators, by an instrument in writing under my, or their, or one of
their hands and seals, should particularly describe and ascertain the
nature of the said Invention, and in what manner the same was to be
performed and cause the same to be filed in the Great Seal Patent Office,
within six calender months next and immediately after the date of the
said Letters Patent.
NOW KNOW YE, that I, the said Wilhelm Haarmann, do hereby
declare the nature of my said Invention, and in what manner the same
is to be performed, to be particularly described and ascertained in and
by the following statement :-
In order to obtain the artificial production of vanillin, the aromatic
principle of vanilla, by means of coniferine or the sap of plants belonging
to the species of conifera, or any other plants related to this family, as an
extract of all those parts of the just mentioned plants containing
coniferine, take either, first, coniferine; or secondly, the sap of the
plants belonging to the species of conifera, or any other plants related to
that family which has been purified or liberated from albumina or other
impurities; or thirdly, an extract of all those parts of the just mentioned
plants containing coniferine; or fourthly, the products obtained from
coniferine by means of fermentation, putrefaction, or similar action, and
treat one or other with oxydizing agents, or some agents of similar
action, such as bichromate of potassium and sulphuric acid, or any other
peroxyde, oxyde, acid, or salts which produce the same effect.
For the first production I use the following method:-Ten parts of
coniferine are dissolved in hot water and the concentrated solution is
allowed to flow slowly into a gently heated mixture of ten parts of
bichromate of potassium, fifteen parts of strong sulphuric acid, and of
eighty parts of water; the whole is heated for about three hours almost
up to the boiling point of the liquid. The vanillin produced in this way
may be isolated either,―
1. By shaking the solution when it has been filtered and become cold
with ether by separating the etheric from the aqueous solution by

page_text: evaporating the ether from the first by distillation, and by purifying the
dark colored residue by repeated crystallisation.
Or 2. By combining with the boiler in which coniferine has been
treated for about three hours with the oxydizing mixture a distillating
apparatus, and then by distilling the contents of the first mentioned
boiler in a current of hot water streams till only one-fifth of their
original volume remains, and by treating the distillate in the before
described manner with ether to obtain a pure product, and by treating
the residue in the same way to obtain the last traces of an impure
vanillin that may be still contained therein. The artificial vanillin can
also be obtained from an aqueous extract of all those parts of conifera
in which coniferine is present.
The just mentioned impure solutions of coniferine (cambial juice or an
extract of plant parts of conifera must be boiled some time for the
separation of the dissolved albumina, filtered, and strongly evaporated.
For a quick but for my purposes sufficiently exact determination of
both the coniferine and sugar which are contained in the concentrated
solutions I evaporate them perfectly in a water bath, and the residue is
dried at one hundred degrees. On every ten parts of what remains in
the concentrated solutions, fifteen parts of bichromate of potassium,
and twenty parts of concentrated sulphuric acid must be taken, and the
quantity of water must be administered, according to the concentration
of the solution. The further process is as above.
The coniferine decomposes under the influence of ferments into sugar
and a crystallized substance which in contact with damp air also changes
slowly and incompletely into vanillin. To obtain vanillin from this
substance quicker I have treated it as well with an oxydizing mixture
of bichromate of potassium and sulphuric acid.
The vanillin obtained and purified in either way is proved in all cases
completely identical to the natural vanillin.
I wish it to be understood that although I have given the proportions
with which I have obtained good results I do not limit myself to such,
as they may be modified.
I claim as novel the artificial production of vanillin by means of
coniferine or the sap of plants belonging to the species of conifera, or

page_text: any other plants related to this family, as an extract of all those parts of
the just mentioned plants containing coniferine.
In witness whereof, I, the said Wilhelm Haarmann, have to this
my Specification set my hand and seal, this Twenty-second day
of August, One thousand eight hundred and seventy-four.