Z-藁本内酯降解产物的UPCL-QTOF-MS和NMR结构鉴定(英文)  

Structure elucidation of degradation products of Z-ligustilide by UPLC-QTOF-MS and NMR spectroscopy

作　　者：左爱华[1] 程孟春[1] 卓荣杰[1] 王莉[1] 肖红斌[1] 

机构地区：[1]中国科学院大连化学物理研究所分离分析重点实验室,辽宁大连116023

出　　处：《药学学报》2013年第6期911-916,共6页Acta Pharmaceutica Sinica

基　　金：supported by the National Science Foundation of China(No.30973873);Key National Science and Technology Specific Projects(No.2009ZX09502-023)

摘　　要：Z-藁本内酯是中药川芎中主要的苯酞类化合物,具有神经保护、抗炎、抗增值及扩张血管等多种药理作用。但Z-藁本内酯在自然条件不稳定且易于降解,限制其研究和应用。本文采用HPLC-UV、UPLC-QTOF-MS和NMR对Z-藁本内酯室温自然光照下的降解行为及降解产物进行考察和鉴定,Z-藁本内酯完全降解后生成5个降解产物,2个降解产物通过与对照品对比确定为洋川芎内酯I和洋川芎内酯H,2个降解产物采用半制备HPLC分离后进行1H和13CNMR解析,确定其结构为(E)-6,7-反式-双羟基藁本内酯和(Z)-6,7-环氧藁本内酯。最后推测了Z-藁本内酯的降解途径,氧化、水解和异构化是主要的降解反应。Z-Ligustilide, a major phthalide isolated from a widely used traditional Chinese medicine Ligusticum chuanxiong, possesses various pharmacological activities including neuroprotective, anti-inflammatory, anti- proliferative and vasorelaxing effects. However, it is unstable and inclined to degrade in natural conditions, which limits its study and application greatly. In this study, degradation behavior of Z-ligustilide and its degradation products stored at room temperature under direct sunlight were investigated and structure elucidated by HPLC-UV, UPLC-QTOF-MS and NMR. Z-ligustilide degradation and total five degradation products were generated and detected. Two degradation products were unequivocally identified as senkyunolide I and senkyunolide H by comparison with reference compounds. Another two degradation products were further isolated by semi-preparative HPLC and structure elucidated as （E）-6, 7-trans-dihydroxyligustilide and （Z）-6, 7- epoxyligustilide by IH and 13C NMR, respectively. The degradation pathways of Z-ligustilide were finally proposed. Oxidation, hydrolysis and isomerization are the major degradation reactions.

关 键 词：Z-藁本内酯 降解产物 UPLC—QTOF-MS 

分 类 号：R917[医药卫生—药物分析学]