内生真菌叶下珠生拟茎点霉的次级代谢产物研究（英文）

从广藿香内生真菌叶下珠生拟茎点霉(PhomopsisphyllanthicolaA658)中分离纯化得到6个聚酮类化合物,分别鉴定为dothioreloneO(1),2-[3,5-二羟基-2-(7-羟基辛酰基)苯基]乙酸(2),dothioreloneM(3),dothioreloneK(4),cytosporoneB(5),和cytosporoneC(6).其中化合物1为新化合物,化合物2为新天然产物,新化合物的结构进一步通过HR-ESIMS,1DNMR和2DNMR等光谱技术确定.此外,对分离所得的化合物进行了体外细胞毒测试,结果表明化合物3～5显示出不同程度的细胞毒活性.     

棠梨枝叶的化学成分研究

从棠梨枝叶(Pyrus pashia Buch.-Ham.ex D.Don)的甲醇提取物中分离得到了17个化合物,采用高分辨质谱、一维和二维核磁共振等现代波谱技术,鉴定上述化合物的结构分别为:pashinin A(1),天麻苷-7-O-顺式咖啡酸酯(2),天麻苷-7-O-反式咖啡酸酯(3),山奈酚-3-O-β-D-(6′′-O-对香豆酸酯)吡喃葡萄糖苷(4),山奈酚-3-O-β-D-(6′′-O-顺式对香豆酰)吡喃葡萄糖苷(5),天麻苷-7-O-对羟基苯甲酸酯(6),熊果苷(7),robustaside B(8),委陵菜酸(9),蔷薇酸(10),槲皮素3-O-β-D-吡喃葡萄糖苷(11),2R,3R-二氢槲皮素(12),木犀草素-4′-O-β-D-吡喃葡萄糖苷(13),芹黄素-4′-O-β-D-吡喃葡萄糖苷(14),5,7,4′-三羟基异黄酮-7-O-β-D-吡喃葡萄糖苷(15),染料木素(16),咖啡酸(17),其中化合物1和2为新化合物,化合物3为新的天然产物.除化合物17外,其余化合物均首次从该植物中分离得到.化合物1～3的抗肿瘤细胞活性实验表明其没有体外肿瘤细胞生长抑制活性(IC50>40μmol L-1);抗HIV病毒(HIV-1IIIB)实验显示:化合物1有极弱的抗HIV-1的活性,化合物4有弱的抗HIV-1的活性.     

网胰藻Hydroclathrus clathratus的化学成分研究

报道从中国南海网胰藻Hydroclathrus clathratus中分离得到3个单体化合物,经过MS,IR,1HNMR,13CNMR(DEPT),HMQC和HMBC等波谱技术鉴定为:(6R,7aS)-6-羟基-4,4,7a-三甲基-2,4,5,6,7,7a-六氢苯并呋喃-2-酮(1),1-(2-脱氧-β-D-呋喃核糖)-5-甲基-1,2,3,4-四氢嘧啶-2,4-二酮(2),尿嘧啶(3),并通过X射线单晶衍射实验确定化合物1的立体结构,其中化合物1是首次从自然界中分离得到.     

厚皮树树皮的化学成分研究

采用各种柱色谱法从厚皮树(Lannea coromandelica)树皮的78%乙醇提取物中分离得到9个化合物。通过理化性质和波谱数据鉴定为:槲皮素-3-O-芸香糖苷(1),豆甾-4-烯-6β-醇-3-酮(2),蒲公英赛酮(3),蒲公英赛醇(4),乙酰蒲公英赛醇(5),5α-豆甾烷-3,6-二酮(6),β-谷甾醇(7),β-胡萝卜苷(8),香草醛(9)。除了化合物(7),其他化合物都是从该植物中首次分离得到。     

海南染木树叶中的蒽醌成分研究

从海南染木树叶乙醇提取物的乙酸乙酯萃取部位分离得到9个蒽醌类化合物,采用高分辨质谱、一维和二维核磁共振等现代波谱技术,鉴定上述化合物的结构分别为:7-羟基-1,2-二甲氧基-6-甲基-9,10-蒽醌(1),1-羟基-3,6-二甲氧基-9,10-蒽醌(2),10,10'-二蒽酮(3),9,10-蒽醌(4),甲基异茜草素(5),虎刺醇(6),2-羟基-3-甲基-9,10-蒽醌(7),3-羟基-1,2-二甲氧基-9,10-蒽醌(8)和3-羟基-1-甲氧基-2-甲酯基-9,10-蒽醌(9).其中化合物1和2为新天然产物,且化合物1的波谱数据迄今未见任何报道.除化合物9外,其余化合物均为首次从该属植物中分离得到.抗菌活性测试显示,化合物2和9对多种菌株具有很好的抑制作用,尤其是金黄色葡萄球菌,最小抑菌浓度(MIC)值均达到0.078μg/mL;化合物1和6对枯草芽孢杆菌、金黄色葡萄球菌显示出与阳性对照环丙沙星相当或者更强的抑制活性.     

野花椒中2个新苯丙素成分的研究

运用正相、反相硅胶柱层析和HPLC对野花椒(Zanthoxylum utile Huang)的化学成分进行研究,并利用现代波谱技术鉴定化合物的结构.从野花椒茎木乙醇提取物中分离得到14个化合物,分别鉴定为robustine(1),香兰子酸(2),dihydroalatamide(3),tembamide(4),N-benzoyltyramine(5),blumenol(6),blumenol C(7),芥子醛(8),(E)-3-(3,4,5-三甲氧基苯基)-2-丙烯醇(9),松柏醇(10),integrifoliodiol(11),两面针氧新木脂素(12),以及两个新的苯丙素类成分,分别命名为野花椒甲素(13)和乙素(14).所有化合物为首次从该植物中分离得到.     

细穗玄参的化学成分

细穗玄参(Scrofella chinensis Maxim)为玄科细穗玄参属独种植物,它是我国特有种,被用作传统中药.从细穗玄参全草中分离并鉴定了7个化合物.利用光谱(MS、NMR、UV)和化学方法分别鉴定为对苯酚(t),对甲氧基苯甲酸(2),5,7,3＇-三羟基-4-甲氧基黄酮(3),3,7-二羟基5,4＇-二甲氧基黄酮(4),5,6,7-三羟基-4＇-甲氧基黄酮(5),熊果甙(6),玉叶金花糖甙酸(7).7个化合物均为首次从该植物中发现.     

云南萝芙木花新吲哚生物碱

从云南萝芙木(Rauvolfia yunnanensis Tsiang)花乙酸乙酯提取物中分离得到9个化合物(其中4个为吲哚类生物碱), 即(18Z)-11-methoxypicrinine(1), caberoline(2), 11-methoxystrictamine(3)和strictamine(4), 以及russulamide(5), ursolic acid(6), urs-12(13)-en-3α-yl acetate(7), β-amyryl nonanoate(8)和β-sitosterol(9); 采用UV, IR, MS和1D, 2D NMR方法对化合物的结构进行了鉴定, 其中化合物1为新吲哚生物碱, 化合物5, 7和8系首次从该植物中分离得到, 但未得到利血平和育亨宾.     

南鹤虱中两个新的倍半萜类化合物（英文）

从中药南鹤虱(Fructus carotae)中分离纯化得到7个倍半萜类化合物,分别鉴定为7-ethoxy-4(15)-oppositen-1β-ol(1),11-乙酰氧基-8β-当归酰氧基-15-甲氧基-4α,5α-环氧愈创木烷-3-酮(2),11-乙酰氧基-8β-丙酰氧基-4-愈创木烯-3-酮(3),1-oxo-5α,7αH-eudesma-3-en-15-al(4),1β-hydroxy-4(15),7-eudesmadiene(5),1β-hydroxy-4(15),5E,10(14)-germacratriene(6),1β-hydroxy-4(15),5-eudesmadiene(7).其中化合物1和2为新的化合物,新化合物的结构进一步通过HR-ESIMS,1D NMR和2D NMR等光谱技术确定.     

岩生石仙桃化学成分研究

采用柱色谱方法首次对岩生石仙桃80%乙醇提取物的乙酸乙酯部位进行分离纯化,利用波谱技术对分离得到的化合物进行结构鉴定。从岩生石仙桃乙酸乙酯部位中分离得到11个化合物,分别鉴定为棕榈酸甲酯(1),油酸甲酯(2),正癸烷(3),1-十二醇(4),β-谷甾酮(5),香草醛(6),4-羟-3,5-二甲氧基苯甲醛(7),3,5-二甲氧基-4-羟基-苯丙酮(8),对羟基苯丙酸甲酯(9),2,5-二甲氧基苯醌(10),ephemeranthoquinone(11)。化合物(1~11)均首次从该植物中分离得到,其中,化合物1~4和9,10首次从石仙桃属植物中分离得到。     

Über Pterinchemie. 69 Mitteilung [1]. Konformationsanalyse von 5,6,7,8-Tetrahydropteroinsäure und 5,6,7,8-Tetrahydro-L-folsäure

Conformational analysis of 5,6,7,8-tetrahydropteroic acid and 5,6,7,8-tetrahydro-L -folic acid In the 360-MHz-¹H-NMR.-spectrum of (6R, S)-9,9-dideuterio-5, 6, 7, 8-tetrahydropteroic acid (racemic) (XIII) (AMX-System, Fig. 4) and (6R, S)-9,9-dideuterio-5, 6, 7, 8-tetrahydro-L -folic acid (diastereomeric) (XVI) the H_a–C(6) and H_a–C(7) show a vicinal coupling constant of 6,7 Hz and the H_a–C(6) and H_e–C(7) one of 3,2 Hz. The first coupling constant provides evidence for an approximate trans-diaxal arrangement of H_a–C(6) and H_a–C(7), and the second for a gauche conformation of H_a–C(6) and H_e–C(7). The tetrahydropyrazine ring in the racemic 5, 6, 7, 8-tetrahydropteroic acid (III) and in the diastereomeric 5, 6, 7, 8-tetrahydro-L -folic acid (XVII) exists therefore in a half-chair conformation with a pseudoequatorial position of the side chain at C(6) (Fig.5).     

The tautomeric forms of cyameluric acid derivatives

The tautomerism of cyameluric acid C6N7O3H3 (1 a), cyamelurates and other heptazine derivatives has recently been studied by several theoretical investigations. In this experimental study we prepared stannyl and silyl derivatives of cyameluric acid (1 a): C6N7O3[Sn(C4H9)3]3 (3 a), C6N7O3[Sn(C2H5)3]3 (3 b), and C6N7O3[Si(CH3)3]3 (4). In order to investigate the structure of 1 a the mono- and dipotassium cyamelurate hydrates K(C6N7O3H2)2 H2O (5) and K2(C6N7O3H)1 H2O (6) were synthesized by UV/Vis-controlled titration of a potassium cyamelurate solution with aqueous hydrochloric acid. Compounds 3-6 were characterized by FTIR and solid-state NMR spectroscopy as well as simultaneous thermal analysis (TGA, DTA). The single crystal X-ray structures of the salts 5 and 6 show that the hydrogen atoms in both anions are localized on the peripheral nitrogen atoms. This indicates-in combination with the solid-state NMR studies-that the most stable tautomer of solid 1 a is the triketo form with C3h symmetry. However, derivatives of both the hydroxyl and the amido tautomers may be formed depending on the substituent atoms: The spectroscopic data and single crystal structures of compounds C6N7O3[Si(CH3)3]3 (4) and the solvate C6N7O3[Sn(C2H5)3]3C2H4Cl2 (3 b') show that the former is derived from the symmetric trihydroxy form of 1 a, while 3 b' crystallizes as a chain-like polymer, which contains the tin atoms as multifunctional building blocks, that is, bridging pentacoordinated Et3SnO2 and Et3SnON units as well as non-bridging four-coordinated Et3SnN units. The cyameluric nucleus is part of the polymeric chains of C6N7O3[Sn(C2H5)3]3C2H4Cl2 (3 b'), by the action of both tautomeric forms of cyameluric acid, the amide and the ester form.     

6-Oxy-(acetyl ethylenediamine) fluorescein, a novel fluorescent derivatization reagent for carboxylic acids and its application in HPLC

A novel fluorescent derivatization reagent for carboxylic acids, 6-oxy-(acetyl ethylenediamine) fluorescein (AEF), was well designed, synthesized, and applied to HPLC. The derivatization reaction with 12 fatty acids, including n-valeric acid (C5), n-hexanoic acid (C6), n-heptanoic acid (C7), n-octanoic acid (C8), n-nonanoic acid (C9), n-decanoic acid (C10), lauric acid (C12), myristic acid (C14), palmitic acid (C16), stearic acid (C18), oleic acid (C18:1), and linoleic acid (C18:2), was completed at 55 degrees C within 40 min. The derivatives of fatty acids were separated on a C18 RP column and detected by fluorescence detection. The LODs attained were 0.4-1.2 nM (S/N of 3). It has been demonstrated that AEF is a prominent derivatization reagent for carboxylic acids which is suitable for HPLC.     

Phenolic constituents of Knautia arvensis aerial parts

A new C-6 flavone glycoside (6), together with seven known compounds, cryptochlorogenic acid (1), chlorogenic acid (2), 2-O-trans-caffeoylhydrocitric acid (3), isovitexin 7-beta-D-glucopyranoside (4), 7,4'-dihydroxy-5-methoxyflavone-6-C-beta-D-glucopyranoside (5), 3,5-O-dicaffeoylquinic acid (7) and 4,5-O-dicaffeoylquinic acid (8), were isolated from the aerial parts of Knautia arvensis. Their structures were elucidated by extensive spectroscopic methods including 1D- (1H, 13C and TOCSY) and 2D-NMR (DQF-COSY, HSQC, HMBC) experiments, as well as ESIMS analysis. Compounds 1, 3-5 and 8 are reported for the first time in Knautia arvensis.     

15N-NMR. Spectra of pterins and folic acid derivatives

¹⁵N-Chemical shifts of a series of 5, 6, 7, 8-tetrahydropterins, 7, 8-dihydropterins and pterins have been measured in acidic solution by means of a probe for 20 mm sample tubes. Included are the relevant data of folic acid (11) , 5, 6, 7, 8-tetrahydrofolic acid (5) and N (5, 10)-metheno-5, 6, 7, 8-tetrahydrofolic acid (6) . The different oxidation states are clearly relected in the chemical shifts of N (5) and N (8). Assignment of the nitrogen resonances was achieved by protonation effects (discrimination between N (1) and N (3)) and with the aid of alkyl substitution at C (6) and C(7), to distinguish between N (5) and N (8).     

Cytotoxic and anti-oxidant activities of lanostane-type triterpenes isolated from Poria cocos

A new lanostane-type triterpene, 29-hydroxypolyporenic acid C (8), was isolated from the dried sclerotia of Poria cocos together with eight other known compounds pachymic acid (1), dehydropachymic acid (2), 3-acetyloxy-16alpha-hydroxytrametenolic acid (3), polyporenic acid C (4), 3-epi-dehydropachymic acid (5), 3-epi-dehydrotumulosic acid (6), tumulosic acid (7), and dehydrotumulosic acid (9). The compounds were identified by spectral analysis and comparison with spectroscopic data reported in the literatures. Although none of the nine (1 to 9) compounds showed promising antioxidant activity, 1 through 6 and 8 showed good cytotoxicity against human lung cancer cell line A549 and human prostate cancer cell line DU145. Interestingly, all these compounds exhibited better cytotoxicity towards A549 than DU145 cells.     

Synthesis and Crystal Structure of a Novel Organic Adduct Nonlinear Optical Material: 3,5-Dinitrobenzonic Acid·ethanolamine (3,5-DNBEA)

The title compound (C2H7NO·C7H4N2O6) has been obtained by the reaction of etha- nolamine with 3,5-dinitrobenzoic acid in deionized water at room temperature. The crystal crystal- lizes in orthorhombic, space group P212121 with a = 6.048(2), b = 9.146(3), c = 21.955(7)(A), C9H11N3O7, Mr = 273.21, Z = 4, V = 1214.3(7)(A)3, Dc = 1.494 g/cm3, F(000) = 568, μ(MoKα) = 0.131 mm-1, R1 = 0.0338 and wR2 = 0.0497. The new organic adduct is composed of one ethanolamine and one 3,5-dinitrobenzoic acid, which are linked up by O-H…O and N-H…O types of hydrogen bonds to form a nine-membered ring and an eleven-membered ring, extending into a one-dimensional network structure.     

Tetranorditerpene lactones, potent antifungal antibiotics for human pathogenic yeasts, from a unique species of Oidiodendron

The culture filtrate of a fungus isolated from decaying Picea glauca wood and tentatively identified as Oidiodendron cf. truncatum showed strong antibiotic activity against the pathogenic yeast, Candida albicans. Four new tetranorditerpenoids, oidiodendrolides A (3), B (4), and C (5) and oidiodendronic acid (7) were isolated along with three known tetranorditerpenoids, LL-Z1271 alpha (= PR1387) (1), PR1388 (2), and acrostalidic acid (6), from rice fermented by the above fungus. The structures of oidiodendrolides A (3), B (4), and C (5) and oidiodendronic acid (7) were established on the basis of spectroscopic and chemical investigations. The antifungal activity of the above tetranorditerpenoids against the pathogenic yeasts, Candida albicans and Cryptococcus neoformans is discussed.     

Crystal Structure of Nicotinic Acid(3,5-dinitrobenzoic Acid Organic Adduct

The title compound nicotinic acid(3,5-dinitrobenzoic acid(NDNT)has been obtained by the reaction of nicotinic acid with 3,5-dinitrobenzoic acid in deionic water at room temperature.The crystal is of monoclinic,space group P21/n with a=14.053(6),b=5.046(2),c=20.105(8)A,β=103.573(8)°,C13H9N3O8,Mr=335.23,Z=4,V=1385.8(10)A3,Dc=1.607g/cm3,μ(MoKα)=0.137 mm－1,F(000)=688,R=0.0435 and wR=0.0993 for 1239 observed reflections (I>2σ(I)).In the crystals,the asymmetric unit contains one nicotinic acid (C6H5NO2)and one 3,5-dinitrobenzoic acid (C7H4N2O6)molecules which are linked by some hydrogen bonds to form a twenty-membered hydrogen-bonded ring and an extended linear structure.     

Synthesis of Novel 8,14‐Secoursane Derivatives: Key Intermediates for the Preparation of Chiral Decalin Synthons from Ursolic Acid

The novel 8,14‐secoursatriene derivative 6 was synthesized starting from ursolic acid ( 1 ) via methyl esterification of the 17‐carboxylic acid group and benzoylation of the 3‐hydroxy group (→ 2 ; Scheme 1), ozone oxidation of the C(12)?C(13) bond (→ 3 ), dehydrogenation with Br₂/HBr (→ 4 ), enol acetylation of the resulting carbonyl group (→ 5 ; Scheme 2), and ring‐C opening with the aid of UV light (→ 6 ). Ring‐C‐opened dienone derivative 7 of ursolic acid was also obtained via selective hydrolysis of 6 (Scheme 2). Both compounds 6 and 7 are key intermediates for the preparation of chiral decalin synthons from ursolic acid.