Studer Joe, Purdie Neil, Krouse Justin A
Department of Chemistry, Oklahoma State University, Stillwater, Oklahoma 74078-0447, USA.
Appl Spectrosc. 2003 Jul;57(7):791-6. doi: 10.1366/000370203322102870.
The rapid Friedel-Crafts chromogenic acylation of alkene groups at ambient temperatures using a 25:1 mixture of 98% acetyl chloride and 70% perchloric acid is shown to have all the properties needed to serve as a potential quality control reagent that can be used to routinely discriminate among steroid analogs. Although ostensibly a non-selective reagent, from these and prior applications in terpenes and polyunsaturated acid esters, it is seen that the reaction is capable of discriminating bewteen geometric isomers and even enantiomers. The selectivity towards acylation of the alpha- over the beta-position at C-17 makes the method adaptable to screening for anabolic steroids. Reactions at that position produce the more unusual results, including a positive color reaction for alpha-methyltestosterone even though there is no alkene functional group in the vicinity of C-17. For molecules with more than one alkene, concurrent acylations are independent one from the other and, in the absence of any interferences, their spectral properties are found to be additive.
使用98%乙酰氯和70%高氯酸的25:1混合物在环境温度下对烯烃基团进行快速傅克显色酰化反应，结果表明该反应具有作为潜在质量控制试剂所需的所有特性，可用于常规区分甾体类似物。尽管表面上是一种非选择性试剂，但从其在萜类化合物和多不饱和酸酯中的这些及先前应用可以看出，该反应能够区分几何异构体甚至对映体。C-17位α-位相对于β-位酰化的选择性使得该方法适用于筛选合成代谢类固醇。该位置的反应产生了更不寻常的结果，包括α-甲基睾酮出现阳性颜色反应，尽管C-17附近没有烯烃官能团。对于含有多个烯烃的分子，同时进行的酰化反应相互独立，并且在没有任何干扰的情况下，发现它们的光谱特性具有加和性。
