秀丽莓干燥茎中的化学成分研究

目的研究秀丽莓(Rubus amabilis Focke)干燥茎中的化学成分,阐明秀丽莓药效物质基础。方法采用水提取、柱色谱法以及结晶法对秀丽莓干燥茎进行分离纯化,用核磁共振、质谱等光谱波谱技术对分离得到的化合物进行结构鉴定,并结合高效液相色谱-离子阱-飞行时间质谱法(LC/MS-IT-TOF)对其中的化学成分进行分析,SunFire~(TM)C_(18)色谱柱(4.6 mm×150 mm,5μm),甲醇(A)-0.5%甲酸水溶液(B)为流动相进行梯度洗脱,电喷雾离子源为质谱离子源,同时采用正、负离子检测模式,获得不同化合物的多级质谱数据。结果从秀丽莓干燥茎中分离出了5个化合物,分别鉴定为1,2,8-三甲氧基-6-羟基酮、2α,3α,19α,23-四羟基-乌苏-12-烯-28-酸、齐墩果酸、(+)-儿茶素及(-)-表儿茶素。根据高分辨质谱结果和MS/MS碎片信息,结合对照品质谱信息及相关文献,共鉴定推断出27个化合物,其中1个酮:1-羟基-3,7,8-三甲氧基酮;1个单萜:7-epiphlomiol;5个二萜类:对映-贝壳杉-16-烯-9-醇、对映-16β,17-二羟基-贝壳杉-19-羧酸、对映-贝壳杉-3α(β),16β,17-三醇、甜茶苷、甜茶单糖苷;9个三萜类:2α,3β,23α-三羟基-乌苏-12,18-二烯-28-酸、2α,3β,23α-三羟基-乌苏-12,19-二烯-28-酸、19α-羟基熊果酸、2α,19α-二羟基-乌苏-12-烯-28-酸、2α-羟基乌苏酸、2α,3α-二羟基-齐墩果-12-烯-28-酸、3β,16α,22α,28-四羟基齐墩果-12-烯、3β,16α,22α,23,28-五羟基齐墩果-12-烯及萎陵菜酸;11个黄酮类:原花青素B1~B8、槲皮素-3-O-β-D-吡喃葡萄糖苷、槲皮素及8,3'-二羟基-7,4'-二甲氧基异黄酮。结论化合物1,2,8-三甲氧基-6-羟基酮为蔷薇科植物中首次分离得到;化合物(+)-儿茶素与(-)-表儿茶素为首次从悬钩子属植物中分离得到;其余化合物为首次从秀丽莓中发现。

Determination and isolation of chemical constituents from the dried stems of Rubus amabilis Focke

Objective To study the chemical constituents from the dried stems of Rubus amabilis (Focke).Method The chemical constituents of R.amabilis were extracted with boiled water,then isolated and purified with various chromatographic columns including silica gel,reversed phase and gelatin chromatography and crystallization methods.The structure was identified by using different spectroscopic and chromatographic techniques including nuclear magnetic resonance and mass spectrum.The liquid chromatography-mass spectrometry-ion trap-time of flight (LC/MS-IT-TOF)method was also applied to analyze the ingredients.The chromatographic separation was performed on SunFireTM C18 column (4.6 mm x 150 mm,5 μm) with gradient elution of methanol (A)-0.5％formic acid aqueous solution (B).Multistage mass spectrometry data of different compounds was obtained by using electrospray ionization source and monitoring in positive and negative ion modes.Results There were 5 chemical constituents isolated from the plant including 1,2,8-trimethoxy-6-hydroxyxanthone,2α,3α,19α,23-tetraydroxy-urs-12-en-28-oic acid,oleanolic acid,(+)-catechin and (-)-epicatechin.Twenty-seven compounds including 5 diterpenoids,1 monoterpenoid,1 xanthone,11 flavones and 9 triterpenoids were identified based on the characteristic MS/MS fragment ions data with chemical standards and published literatures.These constituents were determined to be 1-hydroxyl-3,7,8-trimethoxylxanthone,7-epiphlomiol,ent-kaur-16-ene-9-ol,ent-16β,17-dihydroxy-kauran-19-oic acid,ent-kauran-3α (β),16β,17-triol,rubusoside,rubusoside B,pinfaenoic acid,isopinfaenoic acid,19α-hydroxylursolic acid,2α,19α-dihydroxyl-ursan-12-en-28-oic acid,2α-hydroxylursolic acid,2α,3α-dihydroxyl-oleanan-12-en-28-oic acid,camelliagenin A,camelliagenin C,tormentic acid,procyanidin B1-B8,isoquercitrin,quercetin and kumata kenin.Conclusion Compound 1 was isolated from Rosaceae for the first time.Compounds 20 and 21 were obtained from Rubus firstly.The rest constituents were firstly found from the plant.