Chromatographische differenzierung von cardenoliden durch anwendung von boraten und anderen diolreagenzien

Abstract

The paper probes 13 diol reagents known to interact with the cis-1,2,- and/or -1,3-diol groups of carbohydrates and other compounds, as to their influence on the relative mobilities of 16-acetylgitoxin and acetylgitoxin-α as representative for cis-1,2- and cis-1,3-diols in the cardenolide series. The influence on mobility has been studied using paper partition chromatography with formamide as stationary phase. Metaboric aced, boric acid, arsenic pentoxide, phenyl arsonic acid, ammonium metavanadate, sodium molybdate, and sodium tungstate are without influence on the relative mobilities of both diols. Sodium metaborate, disodium tetraborate, and potassium borooxalate decrease and arsenic trioxide increases specially the mobility of the 1,2-diol. Phenylboronic acid and diphenylborinic acid increase the relative mobility of both diols. In the case of phenylboronic acid a differentiation between both diols is possible: at low concentration the relative mobility of the 1,3-diol only and at high concentration that of the 1,2-diol, too, increases. The effect of the diol reagents is completely lost by acetylation of one OH group of the reacting diol group. Apparently, the reagent's effects on chromatographic mobility are due to the formation of cyclic complexes or cyclic esters with the cis-1,2- or cis-1,3-diol group.