Vandenheuvel F A
J Chromatogr. 1975 Jan 14;103(1):113-34. doi: 10.1016/s0021-9673(00)83806-6.
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 which afford excellent yields of the major products are described. Reactions studied include the Wolff-Kishner removal of keto groups (WK), their conversion to hydroxyl groups by NaBH4(RD), and to dioxolone derivatives by ethylene glycol (DO); the conversion of hydroxyl to keto groups by CrO3 (OX), and to TMS ethers by hexamethyldisilazane; the hydrolysis of dioxolone and TMS derivatives by H+ (HY). GLC chromatograms of reaction mixtures of single and multistep reactions readily provide information on effects on functional groups at positions 3, 11, and 20 in the pregnane series, and the retention times of many steroids unavailable from commercial or 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.
报道了在标准化条件下通过气液色谱法（GLC）观察到的经典反应对甾体的定性和定量影响，包括双内标技术。描述了适用于纳克量反应物的简单程序，这些程序能提供高产率的主要产物。所研究的反应包括通过Wolff-Kishner反应去除酮基（WK）、通过NaBH4将其转化为羟基（RD）以及通过乙二醇将其转化为二氧杂环戊酮衍生物（DO）；通过CrO3将羟基转化为酮基（OX）以及通过六甲基二硅氮烷将其转化为TMS醚；通过H+水解二氧杂环戊酮和TMS衍生物（HY）。单步和多步反应混合物的GLC色谱图能轻松提供有关孕烷系列中3、11和20位官能团影响的信息，以及许多从商业或其他来源无法获得的甾体的保留时间。GLC数据分析提供了甾体结构与保留时间之间的关系，据此设计了计算保留时间和甾体鉴定的方法。证明了计算方法的准确性。
