Abstract
The reaction behavior of condensed tannins and related polyphenols with ammonia (NH3) water was examined. NH3 water treatment of pyrogallol, gallic acid, and epigallocatechin, which have a pyrogallol nucleus, caused regioselective amination in the presence of molecular oxygen (O2) to form 2-aminoresorcinol, 4-amino-3,5-dihydroxybenzoic acid and 4′-C-amino-epigallocatechin, respectively. In contrast, other polyphenols, such as catechol, protocatechuic acid, and epicatechin, which have a catechol nucleus, did not undergo amination even in the presence of O2. Under nitrogen atmosphere (in the absence of O2), epimerization at the C-2 position took place during NH3 treatment of epigallocatechin, in addition to amination. The same epimerization took place during NH3 treatment of epicatechin regardless of the presence or absence of O2. By NH3 treatment, pyrogallol-type B-rings of condensed tannin from Acacia mearnsii underwent regioselective amination to yield 4′-amino-3′,5′-dihydroxybenzene-type B-rings in the presence of O2, whereas catechol-type B-rings of condensed tannin from quebracho showed little amination regardless of the presence or absence of O2. From these results, it was concluded that amination of pyrogallol nucleus by NH3 treatment should proceed via oxidation and reduction, and therefore this reaction would be attributed to the oxidation property of condensed tannins and related polyphenols.