L. Rosenthaler:
Notes on the Behavior of Monohydric Alcohols towards Ferrous Sulfate and Hydrogen Peroxide.
(Communication from the Pharmaceutical Institute of the University of Bern.)
Received on September 10, 1929.
The English chemist Fenton is known to have fundamental valuable studies on the reactions of organic substances with hydrogen peroxide in the presence
of ferrous salts ausr guided. These studies also have a biochemical interest, since we know through the examinations of Warburgs, which role iron
plays in the oxidation processes of the organism.
Now also monohydric alcohols oxidized in the animal organism become an indication of Fenton and Jackson [Ref.1], methyl, ethyl, propyl, isopropyl and
amyl alcohol behave indifferent against Hydrogen peroxide both in the presence and in the absence of Iron and showed completely indifferent behavior,
this requires further research.
The investigation was generally carried out with a fifth of mol. of Alcohol in at least 200g of water (less soluble alcohols in as much water as is
required for complete solution) dissolved, after dissolution of 6 g of ferrous sulfate, 20 g of hydrogen peroxide (30%) were added.
After 24 hours, the reaction was distilled. The distillate was added to calcium carbonate and re-distilled.
With the distillate the reactions of aldehydes employed and the p-Nitrophenylhydrazone was prepared, and from the distillation residues the calcium
and silver salt were produced.
The results were the following:
Methanol: Formaldehyde and formic acid were formed, as evidenced by the usual qualitative reactions.
Ethanol: Acetaldehyde and Acetic acid were detected.
p-Nitrophenylhydrazone, Fp. 128°.
0.0639 g Sbst.: 13.9 ccm N (17°, 711 mm).
Ber.: N 23.47.
Gef.: N 23.48.
Silver salts.
0.2340 g Sbst.: 0.1514 g Ag.
Ber.: Ag 64.64.
Gef.: Ag 64.14.
n-Propanol: n-Propylaldehyde and Propionic acid were detected.
p-Nitrophenylhydrazone.
0.0582 g Sbst.: 12 ccm N (20°, 716 mm).
Ber.: N 21.77.
Gef.: N 22.08.
Silver salts.
Ber.: Ag 59.63.
Gef.: Ag 60.3.
Isopropanol: Acetone (by the reactions of Legal and Deniges, the iodine ammonia reaction u. a.) and acetic acid were detected.
The latter is made of acetone, which, like was found experimentally in the oxidation with hydrogen peroxide and ferrous sulfate, except formic acid,
formaldehyde (indicated by the qualitative reactions) and supplied acetic acid.
For the proof of the acetic acid the calcium salts of the Formic acid and acetic acid-containing solution (see above) with silver nitrate heated until
the acid was completely decomposed to the end. The silver which crystallized from the filtrate became silver and was analyzed.
0.1940 g Sbst .: 0.1255g Ag.
Ber.: Ag 64.64.
Gef.: Ag 64.4.
It may then be considered safe, that also in the oxidation of isopropyl alcohol with hydrogen peroxide and ferrous sulphate, acetic acid is formed.
n-Butyl, iso-Butyl and iso-amyl alcohol can be oxidized by hydrogen peroxide and ferrous sulfate also to aldehydes and acids, as the reductions of
them, and the preparation of p-nitrophenylhydrazones and silver salts, have confirmed.
The analysis did not gave the values normally expected.
It is undoubtedly related to this that the acidic acids present were further oxidized by hydrogen peroxide and ferrous sulfate.
In fact, we know from earlier experiments, from Dakin, that certain fatty acids are already attacked by hydrogen peroxide alone.
The addition of ferrosulphate could only increase the oxidizing strengths at most.
An experiment showed that when butyric acid was oxidised with hydrogen peroxide and ferrous sulfate, a p-Nitrophenylhydrazone compound was obtained
from the distillate.
Conclusion: The monovalent alcohols of methyl to Amyl alcohol are contrary to the data of Fenton and Jackson oxidized by hydrogen peroxide and ferrous
sulfate.
|
But where's the fun in that?