摘要:
利用HPLC,GC/MS和量子化学软件Gaussian 98研究了水溶液中17α-乙炔基雌二醇(EE2)臭氧氧化的产物及反应历程.分析结果表明,水溶液中EE2的氧化产物为亲水性较大的小分子化合物,经臭氧氧化2min后的产物主要为羟基化EE2的醌类化合物,20min后的氧化产物主要为乙二酸、丙二酸等含有2-6个碳原子的小分子羧酸类物质.软件计算结果表明,EE2分子中C2原子的电荷密度比较高,发生羟基自由基加成反应生成羟基化产物,然后被氧化为醌类化合物,进一步的氧化使得EE2苯环和脂环发生开环反应,生成小分子羧酸.产物鉴定与量子化学软件计算的结果具有一致性,两者的结合较好地揭示了EE2臭氧氧化的反应历程.
Abstract:
By using HPLC,GC/MS and quantum chemical calculation software Gaussian 98, the oxidation products and reaction mechanism of 17α-ethinylestradiol (EE2) ozonation in aqueous solutions were investigated. HPLC and GC/MS analysis showed that more hydrophilic products of lower molecular weight formed during ozonation process. Quinone of hydroxylated EE2 was the primary oxidation product after ozonation for 2 minutes, while dicarboxylic acids having 2—6 carbon atoms such as oxilate acid and malonic acid for 20 minutes. Quantum chemical calculation indicated that C atom at C2 position having higher negative charge was attacked by hydroxyl radicals to form hydroxylated EE2 which underwent further oxidation to produce quinone. The quinone was oxidized to break down benzene ring and alicyclic ring to produce carboxylic acids of lower molecular weights. The results indicated the consistence of products identification with quantum chemical calculation by Gaussian 98, the combination of these two methods reveal quite well the reaction mechanism of EE2 ozonation.
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