滇产植物皂素成分的研究——Ⅹ.五指莲的两个新甾体皂甙(1)

从重楼属植物五指莲Paris axialis H.Li.根茎中分离到三个甾体皂甙,经化学降解,质谱,核磁共振谱分析,证明其中两个甙为新的化合物,即偏诺皂甙元-3-O-β-D-葡萄吡喃糖基(1→3)[α-L-鼠李吡喃糖基(1→2)]-β-D-葡萄吡喃糖甙(Ⅰ)和24α-羟基偏诺皂甙元-3-O-β-D-葡萄吡喃糖基(1→3)][α-L-鼠李吡喃糖基(1→2)]-β-D-葡萄吡喃糖(Ⅲ);另一个鉴定为薯芋皂甙元-3-O-β-D-葡萄吡喃糖基(1→3)[α-L-鼠李吡喃糖基(1→2)]-β-D-葡萄吡喃糖甙(Ⅱ)。     

盾叶薯蓣地上部分的三个新甾体皂甙

从盾叶薯蓣Dioscorea zingiberensis Wright地上部分分离鉴定了四个甾体皂甙,经鉴定甙A为约莫皂甙元-3-O-[α-L-鼠李吡喃糖基(1→2)]-β-D-葡萄吡喃糖甙;甙B为24α-羟基约莫皂甙元-3-O-[α-L-鼠李吡喃糖基(1→2)]β-D-葡萄吡喃糖甙;甙C为约莫皂甙元-3-O-[α-L-鼠李吡喃糖基(1→2)][β-D-葡萄吡喃糖基(1→4)]-β-D-葡萄吡喃糖基;甙D为约莫皂甙元-3-O-[α-L-鼠李吡喃糖基(1→2)][β-D-葡萄吡喃糖基(1→3)]-β-D-葡萄吡喃糖甙。前三者为新化合物,分别命名为盾叶皂甙A_1、A_2、A_3(zingiberoside A_1、A_2、A_3),其中盾叶皂甙A_2的甙元为一新甾体皂甙元,命名为盾叶皂甙元(zingiberogenin)。     

屏边三七根茎中的两个新的齐墩果酸皂甙

从屏边三七(Panax stipuleanatus Tsai et Feng)根茎中分离到二个齐墩果烷型新皂甙,命名为屏边三七甙(stipuleanoside)R_1和R_2,其化学结构经光谱分析和化学降解反应,分别确定为齐墩果酸-3-O-β-D-葡萄吡喃糖基(1→3)[α-L-阿拉伯呋喃糖基(1→4)]-β-D-葡萄吡喃糖醛酸甙(1)和齐墩果酸[28-O-β-D-葡萄吡喃糖基]-3-O-β-D-葡萄吡喃糖基(1→3)[α-L-阿拉伯呋喃糖基(1→4)]-β-D-葡萄吡喃糖醛酸甙(3)。     

滇重楼地上部分的甾体皂甙

从滇重楼Paris polyphylla Sm. var. yunnanensis (Fr.) H-M.地上部分分离得到3个甾体皂甙,经光谱测定和化学降解证明其化学结构分别为:偏诺皂甙元3O-α-L-鼠李吡喃糖基(1→2)〔α-L-鼠李吡喃糖基(1→4))-β-D-葡萄吡喃糖甙(A);孕甾-5,16-二烯-3β-醇-20-酮,3β-O-α-L-鼠李吡喃糖基(1→2)〔α-L-鼠李吡喃糖基(1→4)〕-β-D-葡萄吡喃糖甙(B);孕甾-5,16-二烯-3β-醇-20-酮,3β-O-α-L-鼠李吡喃糖基(1→2)〔α-L-鼠李吡喃糖基(1→4)-α-L-鼠李吡喃糖基(1→4)〕-β-D-葡萄吡喃糖甙(C)。甙A、B和C在滇重楼根中尚未发现,甙C系首次从重楼属植物中获得,而甙A具有止血的活性。     

小花棘豆化学成分的研究

从有毒植物小花棘豆(Oxytropis glabra DC.)的地上部分分离得到10种化合物,经光谱分析及理化常数测定,分别鉴定为槲皮素(Ⅰ)、山奈酚(Ⅱ)、3′,7-二羟基-2′,4′-二甲氧基-异黄烷(Ⅲ)、山奈-7-O-α-L-鼠李吡喃糖甙(Ⅳ)、山奈酚-3-O-β-D-葡萄吡喃糖甙(Ⅴ)、山奈酚--O-β-D-葡萄吡喃糖(1→2)-β-D-葡萄吡喃糖甙(Ⅵ)、山奈酚-3-O-β-D-葡萄吡喃糖-7-O-β-D-葡萄吡喃糖甙(Ⅶ)槲皮素-3-O-β-D-葡萄吡喃糖甙(Ⅷ)、杨梅树皮甙(Ⅺ)和3-O-[α-L-鼠李吡喃糖基(1→3)-β-D-葡萄吡喃糖基(1→6)-β-D-葡萄吡喃糖醛酸基]-黄豆醇B(Ⅹ)。上述成分均为首次从该植物中分得。化合物Ⅹ为新化合物。     

无柄新乌檀中的配糖体

从无柄新乌檀乙醇浸膏的正丁醇部位分离得到7个已知配糖体化合物,经波谱分析为：喹诺酸-3-O-β-D-葡萄吡喃糖基(28→1)-β-D-葡萄吡喃糖酯(1),齐墩果酸-(28→1)-β-D-葡萄吡喃糖酯(2),熊果酸-(28→1)-β-D-葡萄吡喃糖酯(3),喹诺酸-3-O-β-D-葡萄吡喃糖基-(1→3)-6-去氧-β-葡萄吡喃糖苷(4),齐墩果酸-3-O-β-D-吡喃木糖基-(1→2)-β-D-葡萄吡喃糖基-28-O-β-D-葡萄吡喃糖酯(5),番木鳖甙(6),7-甲氧基-龙胆苦甙(7)。这些化合物均为首次从该属中分离得到。     

来江藤的苯丙素类配糖体成分

从云南民间药用植物来江藤(Brandisia hancei Hook．f．)的全草中分离到10个化合物,分别鉴定为3,4-二羟基苯乙醇基-O-α-L-鼠李吡喃糖基(1→3)-β-D-(4-O-咖啡酰基)-半乳吡喃糖苷(1),3,4-二羟基苯乙醇基-O-α-L-鼠李吡喃糖基(1→3)-β-D-(2-O-乙酰基-4-O-咖啡酰基)-半乳吡喃糖苷(2),acteoside(3),2’-acetylacteoside(4),poliumoside(5),2’-acetylpohumoside(6),mussaenoside(7),luteolin-7-O-β-D-glucoside(8),luteolin(9)和mannitol(10)。化合物1-6为苯丙素配糖体成分,其中化合物2为新化合物,化合物1为首次从该属植物中获得。关键词：来江藤;苯丙素类配糖体;3,4-二羟基苯乙醇基-O-α-L-鼠李吡喃糖基(1→3)-β-D-(2-O-乙酰基-4-O-咖啡酰基)-半乳吡喃糖苷。     

滇产植物皂素成分的研究——Ⅵ.滇重楼皂甙(2)

从滇重楼干根粉中分离出三个甾体皂甙,鉴定为薯芋皂甙元-3-O-α-L-鼠李吡喃糖(1→2)-β-D-葡萄吡喃糖甙V,偏诺皂甙元-3-O-α-L-鼠李吡喃糖(1→2)-β-D-葡萄吡喃糖甙Ⅵ,偏诺皂甙元-3-O-α-L-鼠李吡哺糖(1→4)-α-L-鼠李吡喃糖(1→4)-〔α-L-鼠李吡喃糖(1→2)〕-β-D-葡萄吡喃糖甙Ⅶ.皂甙Ⅵ和Ⅶ已显示出有趣的生理活性。     

黄毛楤木皂甙的分离鉴定

从黄毛楤木(Aralia decaisneana Hance)根皮分得3种皂甙(Ad-Ⅰ、Ad-Ⅱ、Ad-Ⅲ)和1种由 Ad-Ⅲ水解得到的次级甙(Ad-Ⅳ),经光谱(IR、FAB-MS、~1H-NMR、~(13)C-NMR)和化学分析(酸、碱水解法),分别鉴定为楤木皂甙 A、3-O-[α-L-阿拉伯呋哺糖-(1→4)-β-D-葡萄吡喃糖醛酸]-齐墩果酸甙、3-O-[β-D-半乳吡喃糖-(1→4)-β-D-半乳吡喃糖-(1→3)-β-D-葡萄吡喃糖醛酸]-齐墩果酸-28-O-β-D-葡萄吡喃糖甙、3-O-[-β-D-半乳吡喃糖-(1→4)-β-D-半乳吡喃糖-(1→3)-β-D-葡萄吡喃糖醛酸]-齐墩果酸甙。前两种皂甙系首次从该植物分得,后两种为新化合物。     

旋花茄新鲜果实中的三个甾体皂苷

从茄科食用植物旋花茄(Solanum spirde)的新鲜果实中分离得到3个化合物,其中一个为新成分,经现代波谱学方法鉴定为26-0-β-D-葡萄吡喃糖基-(25R)-呋甾-3β,22ξ,26-三醇-5-烯-3-0-α-L-鼠李吡喃糖基-(1-2)-[3-0-(3-O-乙酰基)-α-L-鼠李吡喃糖基-(1-4)]-β-D-葡萄吡喃糖苷(1).2个已知化合物分别为26-O-β-D-葡萄吡喃糖基-(25R)-呋甾-22ξ-甲氧基-3β,26-二醇-5-烯-3-O-α-L-鼠李吡哺糖基-(1-2)-β-D-葡萄吡喃糖苷(2)和26-O-β-D-葡萄吡喃糖基-(25R)-呋甾-3β,22ξ,26-三醇-5-烯-3-O-α-L-鼠李吡喃糖基-(1-2)-[α-L-鼠李吡喃糖基-(1-4)]-β-D-葡萄吡喃糖苷(protodioscin)(3),均为首次从该植物中分离得到.     

New steroidal saponins of Agave americana

Two new saponins, agavasaponin E and agavasaponin H have been isolated from the methanolic extract of Agave americana leaves and their structures elucidated. Agavasaponin E is 3-O-[β-d-xylopyranosyl-(1→2glc1)-α-l-rhamnopyranosyl-(1→4)-α-l-rhamnopyranosyl-(1→3glc 1)-β-d-glucopyranosyl-(1→4)-β-d-glucopyranosyl-(1→4)-α-d-galactopyranosyl]-(25R)-5α-spirostan-12-on-3β-ol, whereas agavasaponin H is 3-O-[β-d-xylopyranosyl-(1→2 glc 1)-α-l-rhamnopyranosyl-(1→4)-α-l-rhamnopyranosyl-(1→3 glc 1)-β-d-glucopyranosyl-(1→4)-β-d-glucopyranosyl-(1→4)-β-d-galactopyranosyl]-26-O-[β-d-glucopyranosyl]-(25R)-5α-furostan-12-on-3β,22α,26-triol.     

Die flavonolglykoside von Equisetum telmateja

Nine kaempferol glycosides, including the hitherto unkown 3-β-d-(6-O-acetylglucoside)-7-β-d-glucoside and 3-β-d-(6-O-acetylglucoside)-7-α-l-rhamnoside, have been isolated from Equisetum telmateja of European origin.     

Flavonoids from Haplophyllum pedicellatum, H. robustum AND H. glabrinum

Haplophyllum pedicellatum, H. robustum and H. glabrinum all yielded the known compound gossypetin 8,3′-dimethyl ether 3-rutinoside. In addition the first two species afforded isorhamnetin and its 3-rutinoside. A new glycoside, gossypetin 8,3′-dimethyl ether 3-glucoside was obtained from H. pedicellatum together with the 3-malonylrutinoside, 3-malonylglucoside and 3-galactoside of isorhamnetin plus kaempferol 3-malonylglucoside. H. robustum yielded isorhamnetin 7-glucoside and 3-glucoside and quercetin 3-galactoside, while H. glabrinum was found to contain gossypetin 8-methyl ether 3-malonylrutinoside in addition to kaempferol and isorhamnetin 3-glucoside.     

Four new glycosides from the seeds of Cassia obtusifolia

Four new glycosides, including one anthraquinone glycoside (1), one naphthalene glycoside (2), and two naphthopyrone glycosides (3–4), with 10 known compounds (5–14) were isolated from the seeds of Cassia obtusifolia L. The new structures were determined by spectroscopic analysis and chemical transformations.     

Steroidal saponins of Yucca filamentosa: Yuccoside C and protoyuccoside C

Two new saponins, yuccoside C and protoyuccoside C, have been isolated from the methanolic extract of Yucca filamentosa root and their structures elucidated. Yuccoside C is 3-O-[α-d-galactopyranosyl-(1 → 2)-β-d-glucopyranosyl-(1 → 4)-β-d-glucopyranosyl]-(25S)-5β-spirostan-3β-ol, whereas protoyuccoside C is 3-O-[α-d-galactopyranosyl-(1 → 2)-β-d-glucopyranosyl-(1 → 4)-β-d-glucopyranosyl]-26-O-[β-d-glucopyranosy]-(25S)-5β-furostan-3β,22α,26-triol.     

New tetraacetylated iridoid glycosides from Sambucus ebulus L. leaves

Two new minor “Valeriana type” iridoid glycosides (1) and (2) along with 3 known flavonol glycosides [quercetin-3-O-β-glucopyranosyl-7-O-α-rhamnopyranoside (3), quercetin-3-O-β-glucopyranoside (4) and isorhamnetin-3-O-β-glucopyranoside (5)] were isolated from Sambucus ebulus L. leaves. Their structures were unambiguously elucidated by means of 1D- and 2D-NMR, and UPLC-TOF MS. Compound 2 is a rare representative of iridoid diglycosides, containing uncommon ribohexo-3-ulopyranosyl sugar moiety.     

Cardiac glycosides of the root bark of Nerium odorum

In addition to the known odorosides, the β-d-digitaloside and β-d-glucosyl-(1 → 4)-β-d-digitaloside of uzarigenin were isolated from the root bark of Nerium odorum. Odoroside B was obtained in remarkably high yield among the digitoxigenin and uzarigenin glycosides. With the aid of polyamide column chromatography, oleandrigenin β-gentiobiosyl-(1 → 4)-β-d-digitaloside ( = 16-O-acetylneogitostin) was isolated along with other oleandrigenin glycosides.     

红毛五加叶的三萜皂甙

红毛五加（ＡｃａｎｔｈｏｐａｎａｘｇｉｒａｌｄｉｉＨａｒｍｓ）系五加科五加属植物,分布于河北、河南、四川、陕西、甘肃等省,有祛风湿、通关节、强筋骨、治痿痹等功效［１］。其化学成分未见报道。本文报道红毛五加叶的５个三萜皂甙（甙Ⅰ、Ⅱ、Ⅲ、Ⅳ和Ⅴ）的分离鉴定。它们均首次从该属植物发现,其结构如下：　　　　　　　　　　　　　Ｒ１　　　　　　　　　　　　　　Ｒ２　　　　　　　　Ⅰ　ｒｈａｍ－（１→２）－ａｒａ　　　　　Ｈ　　　　　　　Ⅱ　Ｈ　　　ｒｈａｍ－（１→４）－ｇｌｃ－（１→６）－ｇｌｃ　　　　　…     

Triterpene Glycosides in the Leaves of Acanthopanax giraldii

Five triterpene glycosides have been isolated from the leaves of Acanthopanax giraldii Harms (Araliaceae), which are elucidated as: hederagenin-3-O-α-L-rhamnopyranosyl (1→2) -α-L-arabinopyranoside ( Ⅰ ), hederagenin-28-α-L-rhamnopyranosyl- (1→4) -β -D-glu- copyranosyl-(1→6)-β -D-glucopyranosylester ( Ⅱ ), 3-O-α-L-arabinopyranosyl-hederagenin- 28-β -D-glucopyranosyl- ( 1→6 ) -β -D-glucopyranosylester ( Ⅲ ), 3-O-α-L-arabinopyranosyl- hederagenin-28-α-L-rhamnopyranosyl- ( 1→4 ) -β -D-glucopyranosyl- ( 1→6 ) -β -D-glucopyra-nosylester ( Ⅳ ) and 3-O-α-L-rhamnopyranosyl- (1→2) -α-L-arabinopyranosyl-hederagenin-28-α-L-rhamnopyranosyl-( 1→4 )-β -D-glucopyranosyl-( 1→6 )-β -D-glucopyranosylester ( Ⅴ ). All of them are reported in this genus for the first time. Perhaps the findings are valuable for chemotaxonomy of Acanthopanax genus.     

Synthesis of N-Acetylglucosamine Aryl β-Glycosides Catalyzed by Crown Compounds

Glycosylation of various phenols with -D-glucosaminyl chloride peracetate in a solid phase–liquid system catalyzed by crown compounds was studied. The highest yields of aryl -glycosides were observed at room temperature in acetonitrile using anhydrous potassium carbonate as a base. The optimum phenol–glycosyl donor–base–crown ether ratio was 1 : 1 : 1 : 0.2.