Synthetic Tannins, Their Synthesis, Industrial Production and ApplicationGrasser, Georg
Science
Synthetic Tannins, Their Synthesis, Industrial Production and Application
Grasser, Georg
Tannins
It is obtained by extracting myrabolams for one hour and a half, under
reflux condenser, with pyridine, filtering and adding twice the volume
of water to the filtrate and boiling till complete solution is
obtained. After about thirty hours a reddish powder deposits, from which
ellagic acid may be extracted with pyridine; the mother-liquor on being
concentrated yields luteic acid. It is also obtained by oxidising tannin
with hydrogen peroxide, the other oxidation product being ellagic acid,
and the two may then be separated as indicated above. Luteic acid forms
reddish needles which are decomposed, with evolution of gas, at
338°-341° C. Heated with 10 per cent. caustic soda solution it yields
ellagic acid. In pyridine solution the carboxyl group maybe eliminated
by hydrogen iodide, whereby pentoxybiphenylmethylolide is formed as long
silky needles, which do not melt below 300° C. The same substance may
also be obtained when ellagic acid is boiled with concentrated caustic
potash solution. When luteic acid is treated with diazomethane, it
yields the methyl ester of pentamethoxybiphenylmethylolidcarboxylic
acid.
4. DEPSIDES
The most common decomposition products of the natural tannoids are
hydroxybenzoic acids, notably gallic and proto-catechuic acids;
furthermore, other aromatic and aliphatic hydroxy compounds frequently
occur. So far, however, attempts at explaining the constitution of the
complex decomposition products obtained by hydrolysing high molecular
tannoids have not been successful. On the other hand, the constitution
of the simpler natural tannoids is known to a greater or less extent; of
these, lecanoric acid (Lecanorsäure) is the best known, being an ester
anhydride of orsellic acid (a dihydroxytoluylic acid). It combines with
erythrite, forming another tannoid, erythrine. The fact that
hydroxybenzoic acids are constantly encountered together with the
products obtained on hydrolysis of the tannins, seems to point toward
the conclusion that anhydrides of hydroxybenzoic acids are frequent
constituents of the natural tannoid molecules.
The assumption that, for instance, in tannin at least part of the gallic
acid radicals are combined with one another is highly probable, and is
supported by the formation of tri- and dimethylgallic acid from
methylotannin, [Footnote: Herzig, _Monatshefte f. Chemie_, 1909, 30,
343.] and by the formation of ellagic acid when tannin is oxidised.
[Footnote: Nierenstein, _Ber_., 1908, 41, 3015.] Further proof is
brought forward by the existence of the pentacetyl-tannin, [Footnote:
Schiff, _Ann. d. Chem_., 1873, 170, 73.] and by the results of
hydrolysis which has yielded up to 104 per cent. anhydrous gallic acid
fiom tannin [Footnote: Sisley, _Bull. Soc. Chim_. 1909, 5, 727.]
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