Uropygiols: confirmation of structure by proton magnetic resonance

Abstract

Lipids were extracted from excised uropygial glands of domestic chickens and the wax diesters were isolated by preparative thin-layer chromatography (TLC). The diesters were hydrolyzed and the liberated diols were resolved by boric acid TLC into two fractions. These were investigated by proton magnetic resonance at 360 MHz of the free diols and of their acetonide derivatives. The results showed that the cis and trans acetonides, formed from the erythro and threo isomers of the diols, respectively, could be distinguished by the degree of magnetic nonequivalence of the two acetonide methyl groups in each molecule. On the presumption that the cis isomer should show the greater nonequivalence of the methyl groups, this configuration was assigned to the acetonides of these diols which had the lesser TLC mobility on boric acid/silica gel. This agrees with the assignment of configuration made by earlier workers on the basis of the relative TLC mobility of the diol isomers on boric acid/silica gel, but was contrary to a previous assignment based on gas-liquid chromatographic (GLC) retention times. We conclude that the erythro isomers of the diols are characterized by lower mobility on boric acid TLC, as well as on silica gel TLC, and form acetonides that have longer retention times on GLC, and greater nonequivalence of the acetonide methyl groups in the NMR spectrum, than do the acetonides of the threo isomers.