仙茅的化学成分研究

从仙茅(Curculigo orchioides Gaertn．)根茎的乙醇提取物中分离鉴定了7个己知化合物,它们是：eureuligoside I(1),oreinol glueoside(2),3,3′,5,5′-tetramethoxy-7,9′：7′,9-diepoxy-lignan-4,4′-di-O-β-D-glucopyranoside(3),3-hydroxy-5-methyl-phenol-1-O-[β-D-glucopyranosyl-(1→6)-β-D-glucopyranoside](4),2,3,4,7-tetramethoxyxanthone(5),1,3,7-trimethylxanthine(6),daueosterol(7)。其中化合物3～7均为首次从该植物中分离得到。     

仙茅苷丙——仙茅根茎的新酚苷成分

从仙茅(CurculigoorchioidesGaertn.)根茎中分离得到4个化合物,分别为curculigoside(1)、curculigosideB(2)、curculigosideC(3)和2,6-dimethoxylbenzoicacid(4)。其中,化合物3为一个新的酚苷类成分,命名为仙毛苷丙,用现代波谱方法(1H-NMR、13C-NMR、2D-NMR和ESI-MS)鉴定其化学结构为5-羟基-2-O-b-D-吡喃葡萄糖基苄基-3'-羟基-2',6'-二甲氧基苯甲酸酯。     

仙茅苷丙--仙茅根茎的新酚苷成分

从仙茅(Curculigo orchioides Gaertn.)根茎中分离得到4个化合物,分别为curculigoside(1)、curculigoside B(2)、curculigoside C(3)和2,6-dimethoxyl benzoic acid(4).其中,化合物3为一个新的酚苷类成分,命名为仙毛苷丙,用现代波谱方法(1H-NMR、13C-NMR、2D-NMR和ESI-MS)鉴定其化学结构为5-羟基-2-O-β-D-吡喃葡萄糖基苄基-3′-羟基-2′,6′-二甲氧基苯甲酸酯.     

粗枝崖摩中一个新的三萜

从粗枝崖摩(Amoora dasyclada (How et T.Chen)C.Y.Wu)中分离到5个化合物.通过波谱方法鉴定为:24,25-epoxy-tirucall-7-ene-3,23-dione(1),24,25,26,27-tetranortirucall-7-ene-3-oxo-23(21)-lactone(2),taraxerone(3),taraxerol(4)andβ-sitosterol(5).其中化合物1为一个新的三萜,3～5为首次从该植物中分离得到.化合物2是首次从天然植物中分离得到的一个四降三萜,对它的碳谱和氢谱数据进行了全归属.此外化合物2在碳7位上的双键和14位上的甲基并未发生变化,以前文献中没有报道过与此类似的四降三萜,据此进一步讨论了四降三萜的生物合成路径.     

珠子草化学成分的研究

利用大孔树脂吸附和多种柱层析方法,从珠子草中分离得到5个化合物,根据理化数据和波谱学等方法鉴定为柯里拉京(1)、芦丁(2)、isobubbialine(3)、丁二酸(4)和没食子酸(5)。根据2D-NMR修正了化合物3的部分碳信号归属,归属了化合物1的碳氢谱数据。     

益智茎叶中黄酮类化学成分研究

对益智茎叶中黄酮类化学成分进行研究,采用多种色谱方法进行分离纯化,运用多种谱学方法并结合理化性质对分离得到的化合物进行结构鉴定。结果从益智茎叶95%乙醇提取物中共分离得到11个黄酮类化合物,其中包括8个黄酮类化合物,分别鉴定为:良姜素(izalpinin)(1)、杨芽黄素(tectochrysin)(2)、白杨素(chrysin)(3)、芹菜素(apigenin)(4)、刺槐素(acacetin)(5)、5-羟基-4',7-二甲氧黄酮(5-hydroxy-4',7-dimethoxyflavone)(6)、山奈酚-4'-O-甲醚(kaempferol-4'-O-methylether)(7)、5,7,4'-三甲氧基黄酮(5,7,4'-trimethoxyflavone)(8)和3个二氢黄酮类化合物,分别鉴定为:乔松素(pinocembrin)(9)、球松素(pinostrobin)(10)和二氢山萘酚(dihydrokaempferol)(11)。所有化合物均为首次从该植物茎叶中分离得到,其中化合物6、8和10为首次从该属植物中分离得到。     

珠子草中的木脂素类化合物的质谱研究

从珠子草中分离得到了三个木脂素。利用波谱数据(红外光谱、核磁共振和质谱分析)和已知样品的比较鉴定了分离得到的木脂素的结构,详细推测这些化合物的质谱过程,结构表明质谱数据符合化合物的结构特征。     

通光藤甙F,G,H和I结构

从通光藤(Marsdeniatenacissima)的茎中分离得到4个新的C21甾体甙———通光藤甙F(3),G(4),H(5)和I(6),以及2个已知化合物通光藤甙A(1)和B(2)。根据光谱数据和化学方法推定了其结构。同时,通过COLOC谱和二维核磁共振谱指定了这些化合物中甙元上11和12位的酯基确切连接位置。     

金边瑞香有机相提取物库的构建及活性成分分离纯化研究

采用逆流提取-系统溶剂组分化-高效液相色谱法(high-performance liquid chromatography,HPLC)检测组分化效果-高速逆流色谱技术(High-Speed Counter-Current Chromatography,HSCCC)分离制备高纯度化合物的研究思路,对金边瑞香化学成分进行研究得到4个高纯度单体化合物.通过现代谱学方法分别鉴定为:瑞香素(daphnetin,1)、瑞香黄烷I(daphnodorin I,2)、对羟基苯甲酸(p-hydroxybenzonic acid,3)和瑞香黄烷D1(daphnodorin D1,4),化合物2～4均为首次从该种植物中分离得到.     

大果大戟中的一个对映-贝壳杉烷型二萜

从大果大戟的根部首次分离得到一个对映-贝壳杉烷型二萜,利用波谱方法鉴定为ent-16α,17-dihydrox-ykauran-3-one(1)。首次对化合物1在甲醇中的碳谱和氢谱数据进行了全归属。     

Nucleosides. 145. Synthesis of 2,5′-Anhydro-2-Thiouridine and its Conversion to 3′-O-Acetyl-2,2′-Anhydro-5′-Chloro-5′-Deoxy-2-Thiouridine. Studies Directed Toward the Synthesis of 2′-Deoxy-2′-Substituted arabino Nucleosides (7)

Abstract

In an attempt to introduce a substituent at C-2′ in the “up” arabino configuration directly by nucleophilic displacement reaction of a preformed pyrimidine ribonucleoside, we synthesized 2,5′-anhydro-5′-deoxy-2-thiouridine (6) in three steps from uridine. Compound 6 was converted into the 3′-O-acetyl derivative 7. Upon treatment of 7 with triflyl chloride in methylene chloride in the presence of triethylamine and p-dimethylaminopyridine, 2,2′-anhydro-1-(3-O-acetyl-5-chloro-2,5-dideoxy-β-D-arabinofuranosyl)-2-thiouracil (9) was obtained as the only isolable product. Obviously, the intermediate 3′-O-acetyl-2,5′-anhydro-2′-O-triflyl-2-thiouridine (8) was attacked by the chloride nucleophile at C-5′ first giving the 2′-O-triflyl-2-thiouridine intermediate from which 9 was formed by intramolecular nucleopilic reaction.     

Triterpenes and lignans from the leaves of Styrax tonkinensis

Two triterpenes (1 and 2) and eight lignans (3–10) were isolated from the ethyl acetate-soluble fraction of the leaves of Styrax tonkinensis (Pierre) Craib ex Hartw (Styracaceae). Their structures were established as ursolic acid (1), pomolic acid (2), 3,3′-bis(3,4-dihydro-6-methoxy-2H-1-benzopyran) (3), rac-(8α,8′β)-4,4′-dihydroxy-3,3′-dimethoxylignan-9,9′-diyldiacetate (4), (-)-secoisolariciresinol (5), (+)-pinoresinol (6), 4,4′-dihydroxy-3,3′-dimethoxy-9-ethoxy-9,9′-epoxylignan (7), (2S,3R, 4R)-4-[1-ethoxy-1-(4-hydroxy-3-methoxy)phenyl]methyl-2-(4-hydroxy-3-methoxy)phenyl-3-hydroxymethyl-tetrahydrofuran (8), (-)-neo-olivil-(9-O-9″)-seco-isolariciresinol (9) and isolariciresinol (10) based on MS, ¹H-and ¹³C-NMR spectral data. All these compounds (1–10) were firstly isolated from this plant, and compounds 2–5 and 7–9 were reported from the Styrax genus for the first time. Furthermore, the chemotaxonomic significance of the isolated compounds was discussed.     

石菖蒲的化学成分研究

运用色谱法从石菖蒲根茎提取物中分离得到18个化合物,经波谱学分析鉴定为:(7S,8R)-4,9’-di-hydroxyl-3,3’-dimethoxyl-7,8-dihydrobenzofuran-1’-propylneolignan(1),(7S,8R)-4,9’-dihydroxyl-3,3’-dimethoxyl-7,8-dihydrobenzofuran-1’-propylneoligan-9-O-β-D-glucopyranoside(2),7’-hydroxylariciresinol-9-acetate(3),5-羟基-3,7,4’-三甲氧基黄酮(4),野漆树苷(5),紫云英苷(6),松属素-3-O-芸香糖苷(7),山奈酚-3-O-芸香糖苷(8),德钦红景天苷(9),isoschaftoside(10),5-羟甲基糠醛(11),反式桂皮酸(12),3,7-dihydroxy-11,15,23-trioxo-lanost-8,16-dien-26-oicacid(13),3,7-dihydroxy-11,15,23-trioxo-lanost-8,16-dien-26-oic acid methyl ester(14),环阿屯醇(15),胡萝卜苷(16),羽扇豆醇(17),(22E,24R)-ergosta-5,7,22-trien-3β-ol(18)。除化合物4、11和16外,其余15个化合物均为首次从该植物中分离得到。     

柯拉斯那沉香中2-(2-苯乙基)色酮类化学成分研究

为研究柯拉斯那(Aquilaria crassna Pierre ex Lecomte)沉香的化学成分。实验采用多种柱色谱方法从该沉香中分离得到9个2-(2-苯乙基)色酮类化合物,通过现代波谱学技术分别鉴定为6-甲氧基-2-[2-(3′-羟基-4′-甲氧基苯基)乙基]色酮(1)、5-羟基-6-甲氧基-2-[2-(3′-羟基-4′-甲氧基苯基)乙基]色酮(2)、tetrahydrochromone F(3)、6-甲氧基-2-[2-(3′-甲氧基-4′-羟基苯基)乙基]色酮(4)、6-甲氧基-7-羟基-2-[2-(4′-甲氧基苯基)乙基]色酮(5)、6,7-二甲氧基-2-[2-(3′-羟基-4′-甲氧基苯基)乙基]色酮(6)、6,7-二甲氧基-2-[2-(4′-甲氧基苯基)乙基]色酮(7)、6-羟基-2-[2-(4′-羟基苯基)乙基]色酮(8)、5-羟基-2-[2-(2′-羟基苯基)乙基]色酮(9)。化合物2、3和5～9均为首次从柯拉斯那所得沉香中分离得到。采用MTT法对单体化合物的细胞毒活性进行测试,测试结果表明,化合物1,2和4具有微弱的细胞毒活性。     

肋果茶中的萜类化学成分研究

从肋果茶(Sladenia celastrifolia)95％乙醇提取物的乙酸乙酯部位中分离得到15个萜类化合物,经波谱学方法分别鉴定为sladeniafolin A(1),grasshopper ketone (2),(3S,5R,6S,7E,9R) -7-megastigmene-3,6,9-triol (3),hedytriol (4),(3S,5R,6R,7E,9R) -3,5,6,9-tetrahydroxy-7-megastigmene(5),1′S*,4′R*-8-(4′-hydroxy-2′,6′,6′-trimethylcyclohex-2-enyl)-6-methyloct-3E,5E,7E-trien -2-one (6),2α,3α,19α,23-tetrahydroxyurs-12-en-28-oic acid (7),2α,3β,19α,23-tetrahydroxyurs-12-en-28-oic acid(8),pomolic acid(9),3-O-acetyl pomolic acid(10),ursaldehyde (11),camarolide (12),3β-hydroxyurs-11-en-13β(28) -olide (13),3β-hydroxy -11α,12α-epoxy-urs-13β,28-olide (14)和28-0-β-D-glucopyranosyl euscaphic acid (15).以上化合物均首次从该植物中分离得到,其中1为新的C9裂环烯醚萜.     

类芒齿黄芪地下部分化学成分研究

为了解类芒齿黄芪( Astragalus camptodontoides)主要化学成分,从其地下部分甲醇提取物的乙酸乙酯部位分离出19个单体化合物,通过现代波谱分析及理化性质等手段分别鉴定为异补骨脂黄酮(1),4′-hydroxy-isolonchocarpin (2),5-去氧山豆根黄酮(3),shinflavanone (4),khonklonginols H (5),4′-O-methylpreglabridin (6),3′-hydroxy-4′-O-methylglabridin (7),4′-O-methylglabridin (8),8-prenyl-phaseollinisoflavan (9),xambioona (10),光甘草酚(11),粗毛甘草素H (12),methylnissolin (13),邻苯二甲酸异丁酯(14),邻苯二甲酸丁酯异丁酯(15),β-谷甾醇(16),胡萝卜苷(17),齐墩果酸(18),(2S,3S,4R,9E)-1,3,4-trihydroxy-2-[(2′R)-2′- hydr-oxytetraco-sanoylamino]-9-octadecene (19)。化合物1~19均为首次从该植物中获得,化合物1~7为首次从黄芪属(Astraga-lus)植物中分离得到。     

黑柄炭角菌的化学成分

从黑柄炭角菌(Xylaria nigripe)子实体中分离得到10个化合物,通过波谱分析等方法分别鉴定为(22E,24R)-麦角甾-5,7,22-三烯-3β-醇(1)、5α,8α-过氧-(22E,24R)-麦角甾-6,22-二烯-3β-醇(2)、脑苷酯B(3)、脑苷酯D(4)、stearic acid(5)、甘油的亚油酸三酯(trilinolein,6)、α-kojibiose(7)、D-阿洛糖醇(8)、L-氨基丙酸(9)和尿囊素(10)。所有化合物均为首次从该子实体中分离得到。     

云南金钱槭茎化学成分

对云南金钱槭枝条部分的化学成分进行了研究,从其乙醇提取物中共分离鉴定了16个化合物,通过波谱学方法鉴定为:erythro-4,7,9-三羟基-3,3'-二甲氧基-8-O-4'-新木脂素-9'-O-β-D-吡喃葡萄糖苷(1),Hyugano-side IIIa(2),Hyuganoside IIIb(3),erythro-Buddlenol B(4),erythro-7',8'-Didehydrobuddlenol B(5),(±)-丁香脂素(6),臭矢菜素A(7),柑橘苷A(8),(4R)-p-薄荷-1-烯-7,8-二醇7-O-β-D-吡喃葡萄糖苷(9),2-甲氧基-3-(3-吲哚基)丙酸(10),肌苷(11),Tachioside(12),Isotachioside(13),3-O-(β-D-吡喃葡萄糖基)-1-(3,5-二甲氧基-4-羟基苯基)-1-丙酮(14),反式异松柏苷(15),4-[(E)-3-乙氧基-1-丙烯基]-2-甲氧基苯酚(16)。其中化合物5为新的倍半木脂素,其余化合物均首次从该属植物中分离得到。     

Nucleosides. LIV1 Synthesis and Properties of 3′-Azido- and 2′,3′-Dideoxy-6,7-diphenyllumazine Nucleosides

Abstract

The best approach for the synthesis of1-(3-azido-2,3-dideoxy-β-D-erythro-pento-furanosyl)lumazine (5) and its 6,7-dimethyl- (4) and 6,7-diphenyl derivatives (3) has been found in the interconversion of the corresponding 1-(2-deoxy- β-threo-pentofuranosyl)-lumazines. Monomethoxytritylation at the 5′-position (1 7, 3 4, 4 9) followed by mesylation at the 3′-OH group and subsequent nucleophilic displacement by lithium azide afforded 1 9, 2 9 and 4 7 which were deprotected by acid treatment to give 3–5 in good yields. The syntheses of 1-(2,3-dideoxy-β-D-glycero-pentofuranosyl)-6,7-diphenyllumazine (6) and its 6,7-dimethyl derivative (7) were achieved from 1-(2-deoxy-β-D-erythro-pentofuranosyl)-6,7-diphenyllumazine and the corresponding 6,7-dimethyllumazine (2 6) via their 5′-O-p-toluoyl- (2 0, 3 0), and 3′-deoxy-3′-iodo derivatives (2 4, 3 1) to form, after radical dehalogenation and final deprotection, 6 and 7. The newly synthesized lumazine nucleosides have been characterized by elemental analyses, UV-and NMR spectra.     

Lignan glycosides from the Rhizomes of Smilax trinervula and their Biological activities

Phytochemical investigation of the rhizomes of Smilax trinervula led to isolation and structure elucidation of eight lignan glycosides, including five new lignans, namely, (7S, 8R, 8′R)-4, 4′, 9-trihydroxy-3, 3′, 5, 5′-tetramethoxy-7, 9′-epoxylignan-7′-one 4′-O-β-d-glucopyranoside (1), (7S, 8R, 8′R)-4, 4′, 9-trihydroxy-3, 3′, 5, 5′-tetramethoxy-7, 9′-epoxylignan-7′-one 4-O-β-d- glucopyranoside (2) (7S, 8R)-4, 9, 9′-trihydroxy-3, 3′, 5-trimethoxy-4′, 7-epoxy-8, 5′-neolignan 9′-O-β-d-glucopyranoside (3), (7R, 8R)-4, 9, 9′-trihydroxy-3, 5-dimethoxy-7.O.4′, 8.O.3′- neolignan 9′-O-β-d-glucopyranoside (4), and (7S, 8R)-4, 9, 9′-trihydroxy-3, 3′, 5-trimethoxy-8, 4′-oxy-neolignan 4-O-β-d-glucopyranoside (5), along with three known compounds (6-8). Their structures were established mainly on the basis of 1D and 2D NMR spectral data, ESI–MS and comparison with the literature. Compounds 1-8 were tested in vitro for their cytotoxic activity against four human tumor cell lines (SH-SY5Y, SGC-7901, HCT-116, Lovo). Compounds 3 and 5 exhibited cytotoxic activity against Lovo cells, with IC₅₀ value of 10.4 μM and 8.5 μM, respectively.