A New Process of Producing Oxybenzylic Alcohols and their Homologues.
Year: 1894

page_text: Date of Application, 5th Apr., 1894
Complete Specification Left, 19th Dec., 1894-Accepted, 19th Jan., 1895
PROVISIONAL SPECIFICATION.
A New Process of Producing Oxybenzylic Alcohols and their
Homologues.
1, Dr. LEONHARD LEDERER, of 76A I Gabelsbergstrasse, Munich, Germany,
Chemist, do hereby declare the nature of this invention to be as follows:-
Oxycarbonic acids of the aromatic series are known in large number.
As one
part of the same finds an extended technical application, oxyalcohols of the benzol
offered, owing to their close connection with the above mentioned acids, a particular
interest for investigations.
The knowledge of these compounds is however very incomplete and deficient ;
their great capacity of reaction is probably the cause that all the experiments
hitherto made to obtain them synthetically have failed, with few exceptions.
According to my present invention I have found a simple and generally applicable
method for producing members of this class of bodies which consists in putting
phenol or its homologues in reciprocal action, under suitable conditions, with formic
aldehyde.
The reaction process is explained as follows:
An H atom of the benzol core splits off and seizes the atom of the oxygen
of the aldehyde, while at the same time a connection takes place between the
aromatic and aliphatic rest.
1.
11
1 part of phenol and 1 parts of formic aldehyde (commercial aqueous solution)
is allowed to stand at rest, in adding milk of lime (or baryta water), either at
ordinary temperature or, in order to accelerate the reaction, heated to about 60° C.
In the latter case the formation of oxybenzylic alcohol can be proved already
after half an hour.
To obviate the formation of secondary reaction-products, the course of the
reaction is observed by taking from time to time samples, and the action is
interrupted as soon as no further production of oxybenzylic acid takes place.
After neutralization with carbonic acid or acidification with acetic acid,
unaltered phenol is driven off by means of steam, and the oxybenzylic alcohols
are extracted from the residue by means of ether.

page_text: 1 part of phenol and 1½ parts of formic aldehyde are heated to boiling point in
adding zinc powder (or zinc chips, iron powder). The course of the action is in
this case also controlled by taking frequent samples.
When no further formation of oxybenzylic alcohol is perceptible, phenol which
has not entered into reaction is removed by blowing off with steam, and the
oxybenzylic alcohols are taken up from the residue of distillation by means
of ether.
In the same way the homologues of the oxybenzylic alcohols are manufactured.
The oxybenzylic alcohols are colourless, well crystallizing compounds and are
distinguished by their aqueous or alcoholic solutions, giving with ferric chloride
characteristic colour reactions.
ABEL & IMRAY,
Agents for the Applicant.

page_text: A New Process of Producing Oxybenzylic Alcohols and their
Homologues.
I, Dr. LEONHARD LEDERER, of 764 I Gabelsbergstrasse, Munich, 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:-
Oxycarbonic acids of the aromatic series are known in large number. As one
part of the same finds an extended technical application, oxyalcohols of the benzol
offered, owing to their close connection with the above mentioned acids, a particular
interest for investigations.
The knowledge of these compounds is however very incomplete and deficient ;
their great capacity of reaction is probably the cause that all the experiments
hitherto made to obtain them synthetically have failed, with few exceptions.
According to my present invention I have found a simple and generally applicable
method for producing members of this class of bodies, which consists in putting
phenol or its homologues in reciprocal action, under suitable conditions, with
formic aldehyde.
1
The reaction process is explained as follows:-
An H-atom of the benzol core splits off and seizes the atom of the oxygen of
the aldehyde, while at the same time a connection takes place between the aromatic
and aliphatic rest.
The reaction is expressed by the following equation :
The process is carried out in the following manner.
I.
1 part of phenol and 1 parts of formic aldehyde (: commercial aqueous
solution) is allowed to stand at rest, in adding milk of lime (or baryta water) either
at ordinary temperature or, in order to accelerate the reaction, heated to about
60° C. In the latter case the formation of oxybenzylic alcohol can be proved
already after half an hour.
To obviate the formation of secondary reaction products, the course of the
reaction is observed by taking from time to time samples, and the action is
interrupted as soon as no further production of oxybenzylic acid takes place.
After neutralization with carbonic acid or acidification with acetic acid, unaltered
phenol is driven off by means of steam, and the oxybenzylic alcohols are extracted
from the residue by means of ether.

page_text: When no further formation of oxybenzylic alcohol is perceptible, phenol which
has not entered into reaction is removed by blowing off with steam, and the
oxybenzylic alcohols are taken up from the residue of distillation by means of
ether.
In the same way the homologues of the oxybenzylic alcohols are manufactured.
III.
Eugenol and formic aldehyde combine without difficulty in proceeding in the
following manner.
1 part of eugenol, 1 part of formic aldehyde and 1 part of 25 per cent. soda-lye
are allowed to stand at rest at ordinary temperature. The mixture forms a clear
solution, from which after letting stand for several hours crystalline masses are
separated, the quantity of which increases continuously. After two or three days
the action is finished and the reaction mixture is nearly completely solidified to a
hard crystal-cake. The condensation can be accelerated by supplying moderate
heat.
For insulating the product of condensation, which has been separated for the
most part as sodium salt, the reaction mass is directly decomposed by means of
acids, say diluted sulphuric acid, the separated oil is shaken in order to free it from
formic aldehyde admixed thereto, with the necessary quantity of ammonia and
finally after washing out with water, brought to crystallisation. From the several
aqueous solutions a small quantity of the product of condensation may still be
obtained by extracting with ether or benzol.
The new compound, which melts at a temperature of 37° C., is converted by
heating with soda-lye into a substance, the melting point of which is at 87° C.
To produce the latter I proceed more advantageously in the following manner:
1 part of eugenol, 1 part of formic aldehyde and 2 parts of 25 per cent. soda-lye
are heated to the temperature of water-bath. After a short space of time begins
the separation of oil-drops, which increase rapidly and assemble to a layer. The
reaction is finished when the oily layer does no more increase. The mixture
is then acidified and the separated product of condensation is purified by
crystallisation.
The oxybenzylic alcohols are colourless, well crystallising compounds and are
distinguished by their aqueous or alcoholic solutions, giving with ferric chloride
characteristic colour reactions.

page_text: OXYMETHOXYALLYL (1. 2. 4) BENZYLIC ALCOHOLS.
a. Melting point 37° C. Smail leaves or needles. Readily soluble in alcohol,
ether and benzol, but moderately soluble in gasoline. It has a bitter taste and
strongly acid properties; the sodium salt is steady in dry air. It acts in an
anæsthetic and antiseptic manner.
b. Melting point 87° C. Leaves. It is readily absorbed by ether. In benzol
and alcohol it is moderately soluble in the cold, but abundantly in the heat. It
has weakly acid properties.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed, I declare that what I
claim is :-
A process for manufacturing oxybenzylic, oxymethylbenzylic, oxymethylpropyl-
benzylic and oxymethoxyallylbenzylic alcohols consisting in putting phenol, cresol,
thymol or eugenol in reciprocal action with formic aldehyde either alone or in the
presence of condensing agents, substantially as set forth.
Dated this 19th day of December 1894.
ABEL & IMRAY,
Agents for the Applicant.