土田七中化学成分的分离与鉴定

Isolation and Identification of Chemical Constituents from Stahlianthus Involucratus

姜科是多年生草本植物的一个大科,其成员因其可食用性、生物活性和药用活性而引起人们对植物化学的兴趣。姜科植物土田七的根茎在传统医学中一直被用于治疗炎症、疼痛和发烧。为阐明土田七的作用机制和对其进一步开发利用,系统研究土田七的化学成分具有重要意义。目前已经从土田七中分离出卡丹烷二聚体、倍半萜类等化合物,为进一步研究土田七的化学成分,利用半制备型高效液相色谱、柱色谱等多种色谱分离技术对土田七进行了系统分离纯化,并利用高分辨质谱和核磁共振波谱鉴定了所得单体化合物的结构。从土田七75%乙醇提取物的乙酸乙酯部位和正己烷部位中,分离鉴定出了11个化合物,分别为豆甾醇(1)、5,5'–二羟甲基糠醛(2)、顺式–6–甲基–5–亚甲基–3–亚乙基–6–乙酰氧基己二酸(3)、反式–(2R,3S)–2,3–二甲基–5–亚乙基–2–乙酰氧基己二酸(4)、反式–(2R,3S)–2,3–二甲基–5–亚乙基-2-羟基己二酸(5)、2,5–二羟基甲苯(6)、2–乙基–2–丁烯酸(7)、糠酸(8)、反式–4–羟基肉桂酸(9)、千里光宁碱(10)、乙酰化千里光菲林碱(11)。其中化合物3为新化合物,其余化合物为已知化合物。化合物3为无定型粉末,通过质谱数据[M+Na]^(+)=279.0841可确定化合物的分子式为C12H16O6。根据13C NMR谱图和HSQC数据可确定C–H关系,再结合COSY谱可以推断出该化合物的结构。通过1H NMR谱图数据中C–2烯烃质子的化学位移可推测C–2和C–3之间的烯烃为Z型,故命名为顺式–6–甲基–5–亚甲基–3–亚乙基–6–乙酰氧基己二酸。

Zingiberaceae is a large family of the perennial herbaceous plants,members of which have attracted continuous phytochemical interest due to their culinary uses as well as their biological and the pharmaceutical activities.Stahlianthus involucratus is a tropical Zingiberaceae plant and its rhizomes have long been used in traditional medicine to treat inflammation,pain,and fever.In order to clarify the action mechanism of Stahlianthus involucratus and its further development and utilization,systematic study of the chemical composition of Stahlianthus involucratus is of great significance.Previous phytochemical investigations on this species resulted in isolation of cadinane dimers,sesquiterpenoids.In order to further study the chemical constituents of Stahlianthus involucratus,different column chromatographic techniques such as semi-preparative high perfrmance liquid chrmatgraphy and the column chromatography were used to separate and the purify chemical constituents from ethyl acetate fraction and n-hexane fraction of 75%ethanol extract of Stahlianthus involucratus,and the structures of monomer compound were elucidated by mass spectrometry and NMR.Eleven compounds were separated and purified,which were identified as:stigmastern(1),2-hydroxy-1,2-bis[5-(hydroxymethyl)-2-furanyl]ethenone(2),(Z)-2-acetoxy-5-ethylidene-2-methyl-3-methylenehexanedioic acid(3),hexanedioic acid,2-(acetyloxy)-5-ethylidene-2,3-dimethyl-,[R-[R^(*),S^(*)-(Z)]]-(9CI)(4),hexanedioic acid,5-ethylidene-2-hydroxy-2,3-dimethyl-,[R-[R^(*),S^(*)-(Z)]]-(9CI)(5),1,4-dihydroxy-2-methylbenzene(6),2-ethyl-2-butenoic acid(7),2-furoic acid(8),(2E)-3-(4-hydroxyphenyl)-2-propenoic acid(9),senecio-nan-11,16-dione(10),Seneciphyllinine(11).Among these compounds,compound 3 was a new natural product and the others were known compounds.Compound 3 was obtained as a white amorphous powder.Its molecular formula was established as C12H16O6 by mass spectrometry at m/z 279.0841([M+Na]^(+)).The relationship of C-H can be determined by 13C NMR spectrum and HSQC experiments.Combined with the COSY spectrum,the structure of the compound can be inferred.According to chemical shift of the C-2 olefin proton in the 1H NMR spectrum data,it can be inferred that the olefin between C-2 and C-3 is of Z-isomerism.Herein,compound 3 was named as(Z)-2-acetoxy-5-ethylidene-2-methyl-3-methylenehexanedioic acid.