Bertrand M J, Carazzato D, Sarrasin B
Department of Chemistry, University of Montreal, Canada.
J Chromatogr Sci. 1990 Apr;28(4):194-9. doi: 10.1093/chromsci/28.4.194.
A new silylating reagent that forms cyanosyl (cyanoethyldimethylsilyl) derivatives with monohydroxysteroids is introduced and its usefulness for the gas chromatographic analysis of these compounds evaluated. The reactivity of the new reagent, N-methyl-N-cyanoethyldimethylsilyltrifluoroacetamide, has been studied using a series of monohydroxysteroids and compared to that of other reagents forming cyanosyl or alkylsilyl derivatives. The results obtained indicate that at room temperature, in polar solvents, the reagent reacts rapidly and selectively with most hydroxyl groups found in steroids. The cyanosyl derivatives formed have retention properties that are comparable to those of the corresponding alkylsilyl derivatives. However, the former offer advantageous properties for detection since they can be analyzed with a nitrogen-phosphorus detector, and they exhibit mass spectral features that are suitable for identification and quantitation at low levels using selected ion monitoring mass spectrometry. The detection limits for all the monohydroxysteroids studied in this work, as cyanosyl derivatives, are typically on the order of 30-50 pg and the relative response factors are unity within a range of 25 percent.
介绍了一种新型硅烷化试剂，它能与单羟基甾体形成氰基硅烷基（氰基乙基二甲基硅烷基）衍生物，并评估了其在这些化合物气相色谱分析中的实用性。使用一系列单羟基甾体研究了新型试剂N-甲基-N-氰基乙基二甲基硅烷基三氟乙酰胺的反应活性，并与其他形成氰基硅烷基或烷基硅烷基衍生物的试剂进行了比较。所得结果表明，在室温下，在极性溶剂中，该试剂能与甾体中发现的大多数羟基快速、选择性地反应。形成的氰基硅烷基衍生物具有与相应烷基硅烷基衍生物相当的保留特性。然而，前者在检测方面具有优势，因为它们可以用氮磷检测器进行分析，并且它们表现出的质谱特征适用于使用选择离子监测质谱法在低水平下进行鉴定和定量。在这项工作中研究的所有单羟基甾体作为氰基硅烷基衍生物的检测限通常在30 - 50皮克数量级，相对响应因子在25%的范围内为1。
