当归头水提取物中的单萜类成分

Monoterpenes from an aqueous extract of the Angelica sinensis root head

通过大孔吸附树脂、MCI树脂、正相硅胶、Sephadex LH-20和Toyopearl HW-40C柱色谱,结合制备薄层色谱以及反相和手性HPLC分离技术,从“归头”水煎提取物中分离得到11个单萜类化合物,包括2对非等量对映体的7个单萜类新结构化合物或新天然产物以及4个已知衍生物。借助波谱数据分析结合电子圆二色谱(ECD)理论计算和X-射线衍射确定了它们的结构;新结构化合物或新天然产物分别命名为(+)-/(-)-当归单萜酮A和B [(+)-/(-)-1和(+)-/(-)-2]、当归单萜酮C和D (3和4)及当归单萜醇A (5);已知化合物鉴定为6β,9-二羟基-(+)-α-蒎烯(6)、1,1,5-三甲基-2-羟甲基-环己-2,5-二烯-4-酮(7)、jasminol E (8)和(+)-反式水合蒎醇(9)。除6曾在当归地上部分的乙醇提取物中分离得到、本文首次用单晶X-射线衍射确证结构外,其他化合物均为首次从该植物中分离得到。

Eleven monoterpenes including seven new chemical structures or new natural products covering two pairs of scalemic enantiomers,together with four known analogues,were isolated from an aqueous extract of the Angelica sinensis root head(Guitou)by separation techniques of column chromatography over macroporous adsorbent resin,MCI resin,silica gel,Sephadex LH-20,and Toyopearl HW-40C,together with preparative thin-layer chromatography as well as reversed phase and chiral HPLC.Their structures were determined by spectroscopic data analysis,combined with theoretic calculation of electronic circular dichroism(ECD)spectra and single crystal X-ray diffraction.The new structures or new natural products named(+)-/(-)-angelinones A and B[(+)-/(-)-1 and(+)-/(-)-2],angelinones C and D(3 and 4),and angelinol A(5),respectively,while the known analogues were 6β,9-dihydroxy-(+)-α-pinene(6),1,1,5-trimethyl-2-hydroxymethyl-cyclohexa-2,5-dien-4-one(7),jasminol E(8),and(+)-trans-sobrerol(9).All the isolates were reported in this plant for the first time,except for the previously reported 6 from an ethanol extract of the aerial parts of A.sinensis,of which the structure was confirmed by X-ray crystallography in this study.