Synthetic Tannins, Their Synthesis, Industrial Production and ApplicationGrasser, Georg
Science
Synthetic Tannins, Their Synthesis, Industrial Production and Application
Grasser, Georg
Tannins
The elimination of the carbomethoxy group may be brought about by dilute
alkaline solutions in the cold, or by aqueous ammonia. If the depside
formed is so stable as to resist the action of alkali for several hours,
the use of the latter is very convenient for the purpose required. The
substance is dissolved directly in sufficient normal alkali to
neutralise the carboxyl group and a further 2 molecules of caustic soda
for each carbomethoxy group to be eliminated are added. The temperature
should be about 20° C., when the reaction as a rule is completed after
one-half to three-quarters of an hour. It is usual, however, to use an
aqueous ammonia solution in considerable excess, whereby the temperature
should again be about 20° C., and the solution of ammonia normal or half
normal.
The didepsides so far investigated are crystalline bodies, sparingly
soluble in cold water; they--as a rule--decompose when fused, possess
acid reaction, and are dissolved by bicarbonates. On account of the
presence of a free phenolic group they give a coloration with ferric
chloride; if the phenolic group occupies the _o_-position to carboxyl,
the coloration with ferric chloride is red or bluish-violet Excess of
dilute alkali resolved all didepsides into their components at ordinary
temperatures. The didepsides of gallic, proto-catechuic, gentisinic, and
[Greek: b]-resorcylic acids precipitate gelatine and quinine acetate,
and in this respect approach the natural tannins.
The following summary gives an account of depsides which have been
prepared synthetically or which occur naturally:--[Footnote 1: _Ber._,
1908, 41, 2888; 1909, 42, 217; 1913, 45, 2718; 1913, 46, 1130, 2396,
1141, 1143; Liebig's _Ann._, 384, 230, 233, 238; 391, 356, 362.]
Di-_p_-hydroxybenzoic acid.
Di-_m_-hydroxybenzoic acid.
Disalicylic acid.
Diprotocatechuic acid.
Digentisinic acid.
Di-[Greek: b]-resorcylic acid.
_p_-Diorsellic acid.
_o_-Diorsellic acid.
_m_-Digallic acid.
Disyringic acid.
Di-_o_-cumaric acid.
Diferulic acid.
Di-[Greek: b]-hydroxynaphthoic acid.
_p_-Hydroxybenzoyl-_m_-hydroxybenzoic acid.
_m_-Hydroxybenzoyl-_p_-hydroxybenzoic acid.
Salicyl-_p_-hydroxybenzoic acid,
Vanilloyl-_p_-hydroxybenzoic acid.
Feruloyl-_p_-hydroxybenzoic acid.
[Greek: a]-Hydroxynaphthoyl-_p_-hydroxybenzoic acid.
Orsellinoyl-_p_-hydroxybenzoic acid.
Protocatechuyl-_p_-hydroxybenzoic acid.
Galloyl-_p_-hydroxybenzoic acid.
Pyrogallolcarboy _p_-hydroxybenzoic acid.
Syringoyl-_p_-hydroxybenzoic acid.
_p_-Hydroxybenzoyl-syringic acid.
Pentamethyl-_m_-digallic acid.
Pentamethyl-_p_-digallic acid.
Vanilloyl vanillin.
Preparation of Tridepsides
Monohydroxybenzoic acids allow theoretically of tri-depsides of the type
HO.C_6H_4COO.C_6H_4.COO.C_6H_4.COOH only; if, on the other hand, di- or
trihydroxybenzoic acids are dealt with, two formulae are possible,
viz.:--
HO.C_6H_4.COO
} C_6H_3.COOH
HO.C_6H_4.COO
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