Gas-liquid chromatographic studies of reactions and structural relationships of steroids: IV. Substitution in the pregnane side-chain

Abstract

Qualitative and quantitative effects of classical reactions on steroids observed by gas-liquid chromatography (GLC) under standardized conditions, including the double internal standard technique are reported. Simple procedures applicable to nanogram amounts of reactants are described. Reactions studied include the conversion of keto groups to hydroxyl groups by NaBH 4, and to dioxolone derivatives by 1,2-diethanol; 17α-hydroxylation of C20-ketosteroids; the conversion of hydroxyl groups to trimethylsilyl (TMS) ethers by hexamethyldisilazane; the hydrolysis of dioxolone and TMS derivatives by H +. Effects of the Wolff-Kishner reagents, and CrO 3 were also studied. GLC chromatograms of reaction mixtures of single- and multistep reactions readily provide information on effects on functional groups at positions 3, 17, 20, and 21 in the pregnane series, and the retention times of many steroids unavailable from commercial and other sources. GLC data analysis provides relationships between steroid structure and retention time from which methods for the computation of retention times and for steroid identification are designed. The accuracy of the computation methods is demonstrated.