半乳凝素-3潜在抑制剂—1-O-烯丙基-4-O-{3-脱氧-3-[4-苄胺羰基-1H-（1，2，3）三氮唑-1-基]-β-D-吡喃半乳糖基}-2-脱氧-2-乙酰氨基-β-D-吡喃葡萄糖的合成

以乳糖为原料设计合成了半乳凝素-3的潜在抑制剂—1-O-烯丙基-4-O-{3-脱氧-3-[4-苄胺羰基-1H-（1,2,3）三氮唑-1-基]-β-D-吡喃半乳糖基}-2-脱氧-2-乙酰氨基-β-D-吡喃葡萄糖。乳糖2-位的改造采用了叠氮-碘糖基化法,在乙酰氨基引入的同时立体选择性地构建了β-氨基乳糖苷;通过两次构型翻转在3′-位引入叠氮基,然后采用Click反应构建出三氮唑羧基,再与苄胺反应便得到目标物。对乳糖的上述改造旨在提高其对半乳凝素-3的亲和活性。     

乙氧苯柳胺在家兔体内的主要代谢产物

采用高效液相色谱法对家兔口服乙氧苯柳胺（Ｎ－（４－乙氧苯基）－２－羟基苯甲酰胺）后在尿中的代谢物进行了分离与检测．用β－Ｄ－葡糖苷酸酶和该酶加专属性抑制剂葡糖二酸－１，４－内酯分别对尿样进行水解处理，发现该药的主要代谢物为β－Ｄ－葡糖醛酸结合物，其含量超过尿中代谢物总量的８０％．利用色谱保留值和紫外双波长吸收比对酶解后的主要生成物进行定性分析，证明该代谢物为乙氧苯柳胺葡糖醛酸结合物（Ｎ－（４－乙氧苯基）－苯甲酰胺－２－Ｏ－葡糖苷酸）．此外，在家兔给药后０～１２ｈ尿样中未检测出乙氧苯柳胺原形药物及其可能的代谢产物水杨酸．     

Isolation and identification of seven glucuronide conjugates of andrographolide in human urine.

Andrographolide is one of the principal components of a famous traditional Chinese herbal medicine, Andrographis paniculate (Burm) Nees, and has been widely used in the clinic for the treatment of infectious diseases. In this paper, metabolites of andrographolide in the urine of eight healthy volunteers after oral administration were further investigated. Building on previous findings, an additional seven phase II metabolites were isolated by liquid-liquid extraction, open-column chromatography, medium-pressure liquid chromatography, and, finally, preparative high-performance liquid chromatography. Structural elucidation was carried out by mass spectra and NMR spectroscopy including 1H NMR, 13C NMR and two-dimensional NMR (distortionless enhancement by polarization transfer, heteronuclear multiple-quantum correlation, heteronuclear multiple-bond correlation, 1H-1H correlated spectroscopy, and nuclear Overhauser enhancement spectroscopy). All of the metabolites were characterized as glucuronide conjugates, and the structures were determined to be andrographolide-19-O-beta-D-glucuronide (M-1), isoandrographolide-19-O-beta-D-glucuronide (M-2), 14-deoxy-12-hydroxy-andrographolide-19-O-beta-D-glucuronide (M-3), andrographolide-19-O-[6'-methyl-beta-D-glucuronide] (M-4), 14-deoxy-12(13)-en-andrographolide-19-O-beta-D-glucuronide (M-5), 14-deoxyandrographolide-19-O-beta-D-glucuronide (M-6), and 3-oxoandrographolide-19-O-beta-D-glucuronide (M-7), respectively.     

中药黄蜀葵花化学成分的分离与鉴定（III）

目的 研究中药黄蜀葵（Abelmoschus manihot (L.）Medic)花的化学成分。方法 采用正相硅胶、反相ODS、Sephadex LH-20等柱色谱以及HPLC等手段进行分离纯化,并通过理化性质与光谱分析方法鉴定了化合物的结构。结果 从黄蜀葵花体积分数为95%的乙醇提取物中分离鉴定了9个化合物,分别为棉皮素 8-O-β-D-葡萄糖醛酸苷（gossypetin 8-O-β-D-glucuronide,1）、棉皮素 3-O-β-葡萄糖-8-O-β-葡萄糖醛酸（gossypetin 3-O-β-glucopyranoside-8-O-β-glucuronopyranoside,2）、棉皮素 3'-O-β-D-葡萄糖苷（gossypetin 3'-O-β-D-glucopyranoside,3）、tiliroside（4）、山奈酚3-O-[(3"-O-乙酰基-6"-O-(E)-对羟基桂皮酰基)]-β-D-葡萄糖苷（kaempferol 3-O-[3"-O-acetyl -6"-O-(E)-p-coumaroyl)]-β-D-glucopyranoside,5）、槲皮素 3-O-[β-D-木糖基(1→2)-a-L-鼠李糖基(1→6)]-β-D-半乳糖苷（quercetin 3-O-[β-D-xylopyranosyl(1→2)-a-L-rhamnopyranosyl(1→6)-β-D-galactopyranoside,6）、4-羟基苯甲酸 β-D-葡萄糖酯（4-hydroxybenzoic acid β-D-glucose ester,7）、原儿茶酸（protocatechuic acid,8）、原儿茶酸 3-O-β-D-葡萄糖苷（protocatecheuic acid 3-O-β-D-glucoside,9)。结论 其中化合物2、4-9为首次从秋葵属中分离得到,并首次报道了化合物5、6、9在DMSO-d₆中的光谱数据。     

Isolation and identification of metabolites of osthole in rats

Osthole (Ost), one of the major components of Cnidium monnieri (L.) Cusson, is had the structure of an isopentenoxy-coumarin with a range of pharmacological activities. In the present study, the metabolism of Ost in male Sprague-Dawley rats was investigated by identifying Ost metabolites excreted in rat urine. Following an oral dose of 40 mg/kg Ost, 10 phase I and 3 phase II metabolites were isolated from the urine of rats, and their structures identified on the basis of a range of spectroscopic data, including 2D-NMR techniques. These metabolites were fully characterized as 5'-hydroxyl-osthole (M-1), osthenol (M-2), 4'-hydroxyl-osthole (M-3), 3, 5'-dihydroxyl-osthole (M-4), 5'-hydroxyl-osthenol (M-5), 4'-hydroxyl-2', 3'-dihydro-osthenol (M-6), 4'-hydroxyl-osthenol (M-7), 3, 4'-dihydroxyl-osthole (M-8), 2', 3'-dihydroxyl-osthole (M-9), 5'-hydroxyl-2', 3'-dihydroosthole (M-10), osthenol-7-O-β-D-glucuronide (M-11), osthole-4'-O-β-D-glucuronide (M-12) and osthole-5'-O-β-D-glycuronate (M-13). This is the first identification of M-1, M-3 to M-13 in vivo. On the basis of the metabolites profile, a possible metabolic pathway for Ost metabolism in rats has been proposed. This is the first systematic study on the phases I and II metabolites of 8-isopentenoxy-coumarin derivative.     

中药半枝莲黄酮类成分的分离与结构鉴定

目的对中药半枝莲(Scutellaria barbata D.Don)全草的化学成分进行研究。方法应用大孔树脂、正相硅胶、反相ODS、Sephadex LH-20以及制备型高效液相等色谱法对中药半枝莲的化学成分进行了分离;并通过理化性质和光谱数据对化合物的结构进行了鉴定。结果分离鉴定了7个黄酮类化合物,分别为芹菜素(apigenin1,)、木犀草素(luteolin,2)、5,7,4'-三羟基-8-甲氧基黄酮(5,7,4'-trihydroxy-8-methoxyflvone,3)、芹菜素-7-O-β-D-葡萄糖醛酸苷(apigenin-7-O-β-D-glucuronide,4)、芹菜素-7-O-β-D-葡萄糖醛酸甲酯(apigenin-7-O-β-D-glucuronide methyl ester,5)、芹菜素-7-O-β-D-葡萄糖苷(apigenin-5-O-β-D-glucopyranoside,6)、山奈酚-3-O-β-D-芦丁糖苷(kaempferol-3-O-β-D-rutino-side,7)。结论化合物4-7为半枝莲植物中首次分离得到。     

板栗花的化学成分

目的对板栗花的化学成分进行分离和结构鉴定。方法采用硅胶柱色谱、凝胶柱色谱和重结晶等分离方法对板栗花体积分数为90%的乙醇溶液提取物进行化学分离;通过谱学分析方法结合化合物理化性质对化合物结构进行鉴定。结果分离得到11个化合物,分别鉴定为2α,3β,23-三羟基齐墩果烷-12-烯-28-酸(2α,3β,23-trihydroxyolean-12-en-28-acid,1)、4-喹啉酮-2-羧酸-正丁基酯(4-quinolinone-carboxylic-2-acidn-butyl ester,2)、槲皮素-3-O-β-D-半乳糖苷(quercetin-3-O-β-D-ga-lactopyranoside,3)、山柰酚(kaempferol,4)、槲皮素(quercetin,5)、山柰酚-3-O[6″-O-反式-对-香豆酰基]-β-D-吡喃葡萄糖苷(kaempferol-3-O-[6″-O-(E)-p-coumaroyl]-β-D-glucopyranoside,6)、山柰酚-3-O-[2″,6″-O-双-反式-对-香豆酰基]-β-D-吡喃葡萄糖苷(kaempferol-3-O-[2″,6″-di-O-(E)-p-coumaroyl]-β-D-glucopyranoside,7)、没食子酸(gallic acid,8)、原儿茶酸(protocatechuic acid,9)、5-羟甲基糠醛(5-hydroxymethylfurfuraldehyde,10)、槲皮素3-O-β-D-葡萄糖醛酸甲酯(quercetin-3-O-β-D-glucuronide6″-methyl ester,11)。结论化合物1,2,11为从栗属植物中首次分离得到,化合物3为从该植物中首次分离得到。     

加压制备色谱技术结合HPLC指纹图谱导向快速分离制备红花提取物中的主要黄酮类成分（英文）

以HPLC指纹图谱为导向,应用中压反相硅胶柱色谱以及半制备高压液相色谱两种方法,对红花提取物中主要化合物进行快速分离。共分离得到了12个化学成分,包括9个黄酮醇类（1–9）和3个查尔酮类（10–12）。经波谱解析并与文献数据相比对,鉴定其结构分别为：山柰酚3-氧芸香糖苷（1）,山柰酚3-氧葡萄糖苷（2）,芦丁（3）,槲皮素3-氧葡萄糖苷（4）,6-羟基山柰酚3,6,7-三氧葡萄糖苷（5）,6-羟基山柰酚3-氧葡萄糖苷（6）,6-羟基山柰酚6,7-二氧葡萄糖苷（7）,6-羟基山柰酚3-氧芸香糖苷（8）,6-羟基山柰酚3,6-二氧葡萄糖苷7-氧葡萄糖醛酸苷（9）,异红花黄色素C（10）,红花黄色素C（11）,羟基红花黄色素A（12）。结果表明,加压制备色谱结合指纹图谱导向分离是制备靶标化合物一种快速高效的技术手段。     

骨碎补的化学成分

目的研究骨碎补(Drynaria fortunei)的化学成分。方法采用硅胶柱色谱、SephadexLH-20柱色谱、中低压ODS柱色谱及制备液相等方法进行分离纯化,并根据化合物的理化性质及波谱数据对结构进行鉴定。结果从骨碎补中分离并鉴定9个化合物:柚皮苷(1)、木犀草素-7-O-β-D-葡萄糖醛酸苷(2)、咖啡酸-4-O-β-D-吡喃葡萄糖苷(3)、4-O-β-D-吡喃葡萄糖基香豆酸(4)、对羟基反式肉桂酸(5)、反式桂皮酸(6)、3,4-二羟基苯甲酸(7)、5-羟甲基糠醛(8)、蔗糖(9)。结论化合物2、5、6、8和9为首次从槲蕨属植物中分离得到。     

Syntheses of 23-C-alkylidene, and 23-N-containing derivatives of 5-O-mycaminosyltylonolide

Several derivatives of 5-O-mycaminosyltylonolide substituted at C-23 have been prepared; these are 23-deoxy-23-C-methylene (3), 23-deoxy-23-C-(methoxycarbonylmethylene) (5), 23-deoxy-23-C-(ethoxycarbonylmethylene) (7), and 23-deoxy-23-C-(butoxycarbonylmethylene) (9), 23-deoxy-23-C-[(2E)-3-(ethoxycarbonyl)-2-propenylene] (11), and 23-deoxy-23-(dimethylaminoimino) (13), and 14-de(hydroxymethyl)-14-nitrile (16) derivatives. The key steps in these syntheses are the reactions of 2',4'-di-O-acetyl-3-O-tert-butyldimethylsilyl-23-deoxy-23-oxo-5-O- mycaminosyltylonolide diethyl acetal (1) with several Wittig reagents, 1,1-dimethylhydrazine and hydroxylamine. Antibacterial activities of these compounds are also described.     

杠板归化学成分的分离与鉴定

目的对杠板归(Polygonum perfoliatumL.)的化学成分进行分离与鉴定。方法对杠板归体积分数为70%的乙醇提取物的乙酸乙酯萃取部分和正丁醇萃取部分进行分离,通过理化性质和波谱分析鉴定化合物的结构。结果得到7个化合物,分别鉴定为山萘酚(kaempferol,1)、槲皮素(quercetin,2)、蓄苷(avicularin,3)、槲皮素-3-O-β-D-葡萄糖醛酸甲酯(quercetin-3-O-β-D-glu-curonide 6-″methyl ester,4)、槲皮素-3-O-β-D-葡萄糖醛酸正丁酯(quercetin-3-O-β-D-glucuronide 6″-butyl ester,5)、山萘酚-3-O-芸香糖苷(kaempferol-3-O-rutinoside,6)、芦丁(rutin,7)。结论化合物5为首次从该属植物分离得到;化合物3、67、为首次从该植物中分离得到。     

土槿皮的化学成分研究(英文)

对松科Pinaceae植物金钱松Pseudolarix kaempferi Gord的干燥根皮—土槿皮的化学成分进行了研究。应用硅胶,Sephadex LH-20,MCI柱色谱以及高效液相色谱等技术进行分离纯化,利用化合物的理化常数和波谱数据鉴定其结构。分离并鉴定了26个化合物,分别为:土槿丁酸(1),土槿甲酸(2),土槿乙酸(3),土槿丙酸(4),3β-乙酰氧基-齐墩果烷-11,13(18)二烯(5),3β-乙酰氧基-齐墩果烷-9(11),12二烯(6),3β-羟基-齐墩果烷-11,13(18)二烯(7),3β-羟基-齐墩果烷-9(11),12二烯(8),Celangulatin C(9),Celangulatin E(10),17β-通关藤苷元B(11),11α-O-(2-甲基丁酰基)-12β-O-乙酰基通关藤苷元B(12),11α-O-(2-甲基丁酰基)-12β-O-巴豆酰基(顺芷酰基)通关藤苷元B(13),β-谷甾醇酯(14),伞形花内酯(15),5,7-二羟基香豆素(16),花椒毒素(17),异虎耳草素(18),芒柄花黄素(19),毛蕊异黄酮(20),Cnidimol B(21),胸腺嘧啶(22),3-呋喃甲酸(23),2-呋喃甲酸(24),香草酸(25),原儿茶酸(26)。其中化合物5–24为首次从该植物中分离得到;并首次归属化合物1的1H和13CNMR谱数据。     

Metabolism of (2S)-pterosin A: identification of the phase I and phase II metabolites in rat urine

The metabolic profile of the potent hypoglycemic agent, (2S)-pterosin A (1), in rat urine via intragastrical oral administration was investigated. In total, 19 metabolites (M1-M19) were identified. Among these, 16 metabolites were characterized by high-performance liquid chromatography solid-phase extraction-tube transfer-NMR, and seven metabolites were further isolated from the treated urine to enable further structural determination. Twelve of these are new compounds. The phase I metabolites of 1 were formed via various oxidations at positions C-3, C-10, C-12, C-13, or C-1 followed by decarboxylation of C-10 or C-14, and lactonization at C-12/C-14 or C-14/C-12. The phase II metabolites were glucuronide conjugates from the parent compound or phase I metabolites. The major metabolites were found to be (2S)-14-O-glucuronylpterosin A (M9), (2S)-2-hydroxymethylpterosin E (M14), and (±)-pterosin B (M19). Quantitative HPLC analysis of metabolites, based on similar UV absorption and use of the regression equation of 1, indicated that ～71% 1 was excreted as metabolites in rat urine.     

毛菊苣中山柰酚-3-O-β-D-葡萄糖醛酸苷和山柰酚-3-O-β-D-吡喃葡萄糖苷对照品的制备研究

目的建立维药毛菊苣中山柰酚-3-O-β-D-葡萄糖醛酸苷和山柰酚-3-O-β-D-吡喃葡萄糖苷对照品的制备分离方法。方法取毛菊苣药材醇提浸膏的乙酸乙酯萃取部位上样于硅胶柱色谱分离,收集黄酮苷富集流份,继续用凝胶柱色谱及制备HPLC进行分离纯化,通过NMR、MS等波谱方法鉴定化合物结构,经TLC、HPLC-UV及MS联用等技术进行质量分数检测。结果制备分离得到2个化合物分别鉴定为山柰酚-3-O-β-D-葡萄糖醛酸苷(1)和山柰酚-3-O-β-D-吡喃葡萄糖苷(2),质量分数均大于98%,其中2为首次从该属植物中分离得到。结论该法制备得到的2个黄酮苷类对照品符合中药化学对照品的相关技术要求,为药材毛菊苣和含毛菊苣的成方制剂的质量控制及药效物质基础研究提供化学对照品。     

Four new dammarane-type triterpene saponins from the stems and leaves of Panax ginseng and their cytotoxicity on HL-60 cells

Four new triterpene saponins, ginsenosides Rh(14)-Rh(17)(1- 4), along with two known compounds, 20(S)-ginsenoside Rg? and dammar-(E)-20(22),24-diene-3 β,6 α,12 β-triol, were isolated from the stems and leaves of Panax ginseng. The structures of the new compounds were elucidated as 3 β,6 α,12 β,24 ξ-tetrahydroxy-dammar-(E)-20(22),25-diene 6- O- α- L-rhamnopyranosyl-(1?→?2)- β-D-glucopyranoside (1), 3 β,12 β,24 ξ-trihydroxy-dammar-(E)-20(22),25-diene 3- O- β- D-glucopyranosyl-(1?→?2)- β-D-glucopyranoside (2), 3 β,6 α,12 β-trihydroxy-dammar-(E)-20(22),24-diene 3-O-β-D-glucopyranoside (3), and 3-oxo-6 α,12 β,20(S)-trihydroxy-dammar-24-ene 6-O-α-L-rhamnopyranosyl-(1?→?2)-β-D-glucopyranoside (4) by means of extensive spectroscopic and chemical methods, respectively. The isolated compounds were tested for IN VITRO cytotoxicity against HL-60 cells.     

Two new triterpenoid glycosides from the leaves of Anthocephalus chinensis

Nine compounds were isolated from the leaves of Anthocephalus chinensis by column chromatography on silica gel and Sephadex LH-20, and their structures were elucidated by spectroscopic techniques as clethric acid-28-O-β-d-glucopyranosyl ester (1), mussaendoside T (2), β-stigmasterol (3), hederagenin (4), ursolic acid (5), clethric acid (6), 3β,6β,19α,24-tetrahydroxyurs-12-en-28-oic acid (7), mussaendoside I (8), and cadambine (9). Compounds 1 and 2, and 7 and 8 were isolated from the plants of this genus for the first time, and compounds 1 and 2 were new triterpenoid glycosides.     

Properties and Reactions of Substituted 1,2-Thiazetidine 1,1-Dioxides: Fluoride Catalyzed Reactions of Silylated β-Sultams with Electrophiles

N-Silylated β-sultams 1 and 4 react with ketones and aldehydes in the presence of fluoride ions to O-silylated carbinolsulfonamides 3 . Under similar conditions, N-aminoalkylated 4-silylated β-sultams react to O-silylated C-4 aldol adducts 7 , which are deprotected and desilylated to 8 and 10 . The (α-hydroxy-α-methylethyl)-substituted β-sultam 16 is prepared from 14 via 15 . Reactions of 5b and 14 with aromatic aldehydes yield the Peterson olefination products 11, 12 , and 19 . E- and Z-isomers of these compounds are separated by CC.     

喙柱牛奶菜抗生育成分的研究

从喙柱牛奶菜Marsdenia oreophila甲醇提取物中获得一孕甾四糖甙,经化学反应,波谱分析,酸碱降解及水解确定其结构,命名为喙柱牛奶菜甙乙(marsdeoreophisideB,II),并证明为新化合物,动物实验初步证明该物有抗早孕活性。     

草苁蓉化学成分的研究

目的：研究我国民间草药草苁蓉［Boschniakia rossica (Cham.et Schltdl) Fedtsch.et Flerov.］的化学成分。方法：草苁蓉全草醇提取物的乙酸乙酯部位经硅胶柱色谱和制备薄层分离,分得8个化合物。通过波谱和化学方法鉴定了它们的结构。结果：8个化合物的结构分别鉴定为4,5,6-三羟基噢酮(1)、β-谷甾醇(2)、β-谷甾醇3-O-β-D-葡糖苷(3)、7-去氧-8-表马钱子酸(4)、没食子酸(5)、肉桂酸(6)、咖啡酸(7)和草苁蓉纳拉苷(8)。结论：4,5,6-三羟基噢酮(1)为新的噢酮化合物,4个已知化合物:7-去氧-8-表马钱子酸(4)、没食子酸(5)、肉桂酸(6)、咖啡酸(7)为首次从草苁蓉中分得。     

Dentatins: Sesquiterpene glucosides fromIxeris dentata

Three new sesquiterpene lactone glucosides named dentatins A, B and C were isolated fromIxeris dentata and the structures were elucidated as 3β, 8β-dihydroxy-(1α, 5α)-guaian-10(14)-ene-6α, 12-olide-3-O-β-D-glucopyranoside (1), 3β, 8β-dihydroxy-(1α, 5α)-guain-4(15), 10(14)-diene-6α, 12-olide-3-O-β-D-glucopyranoside (2) and 3β, 9β-dihydroxy-(1α, 5α)-guaian-4(15), 10(14)-diene-6α, 12-olide-3-O-β-D-glucopyranoside (3), respectively, on the basis of spectral evidence.