Benzyl esters of C 2—C 20 fatty acids and metabolically relevant carboxylic acids : Preparation and gas chromatography—mass spectrometry

Abstract

Short-, medium- and long-chain fatty acids, and other types of metabolically relevant carboxylic acids like hydroxy-, keto-, aromatic and dicarboxylic acids, were analyzed by capillary gas chromatography. For separation, benzyl ester derivatives were used, prepared by reaction of the potassium carboxylates with benzyl bromide in acetonitrile catalyzed by a crown ether. The reaction conditions for quantitative benzylation were studied. Keto groups of ketocarboxylic acids were stabilized prior to benzylation by formation of O-methyl oximes using methoxyamine hydrochloride in aqueous—ethanolic solution. The separation of more than 45 carboxylic acids was achieved on a CP-Sil 5 CB fused-silica capillary column in less than 70 min. The electron impact mass spectra of ketocarboxylic acid O-methyl oxime benzyl esters and some hydroxycarboxylic acid benzyl esters are discussed.