论文部分内容阅读
为探讨新鱼腥草素钠缩合反应机制并鉴定稳定化缩合产物的化学结构,制备了二聚物并进行转化反应,采用LC-DAD-MS/MS联用技术分析转化产物的紫外吸收特征及质谱信息,采用紫外分光光度法考察转化动力学及转化半衰期。经有机溶剂萃取及柱层析分离纯化,制备了稳定化缩合产物对照品,采用红外、高分辨质谱和核磁共振技术进行结构鉴定,并将LC-MS/MS分析结果与二聚物转化产物进行比较。二聚物结构不稳定,在水溶液中易解离生成游离的十二酰乙醛,进而发生三分子环合加成?原位脱水缩合反应,生成含六元环稳定结构的1,3,5-三-(十二烷酰基)-苯(三聚物),转化反应符合二级动力学方程,25℃(298K)和100℃(373k)条件下转化半衰期分别为3.17h和6.39min。二聚物系缩合过程中的中间过渡状态,推测新鱼腥草素钠注射液中的缩合产物主要以三聚物的形式存在。
In order to explore the mechanism of sodium hypochlorite condensation reaction and identify the chemical structure of the stabilized condensation products, dimers were prepared and transformed. The UV absorption characteristics of the products were analyzed by LC-DAD-MS / MS. Mass spectrometry information, conversion kinetics and half-life of conversion were examined by UV spectrophotometry. After purification by organic solvent extraction and column chromatography, the reference substance of the stabilized condensation product was prepared and identified by IR, high resolution mass spectrometry and nuclear magnetic resonance spectroscopy. The LC-MS / MS analysis was carried out with the dimer conversion product Compare Dimer structure instability, easy to dissociate in aqueous solution to generate free lauroyl acetaldehyde, and then occur three-ring cyclization addition? In-situ dehydration condensation reaction to generate a stable structure with six-membered ring 1,3,5 - tris (dodecanoyl) -benzene (terpolymer). The conversion reaction accorded with the second-order kinetic equation. The conversion half-lives at 25 ℃ (298K) and 100 ℃ (373k) were 3.17h and 6.39min, respectively. Dimeric condensation system in the middle of the transition state, it is speculated that sodium oxyfoe sodium injection condensation products mainly exist in the form of trimers.