海洋真菌赤褐炭团菌FS521的次级代谢产物研究（英文）

从海洋真菌赤褐炭团菌(Hypoxylon rubiginosum) FS521中分离纯化得到17个聚酮类化合物,分别鉴定为4-乙酰氧基-8-甲氧基-3,4-二氢萘-1(2H)-酮(1)、4,8-二甲氧基-1-萘酚(2)、1'-羟基-4',8,8'-三甲氧基[2,2']联萘-1,4-二酮(3)、3,6-dimethyl-atromentin (4)、4-羟基-8-甲氧基-3,4-二氢萘-1(2H)-酮(5)、regiolone (6)、methylsclerone (7)、5-methylmellein(8)、3,5-二甲基-8-甲氧基-3,4-二羟基异香豆素(9)、9-甲氧基萘(10)、1,8-二甲氧基萘(11)、8-甲氧基-1-萘醇(12)、7-甲氧基-3-甲基异苯并呋喃(13)、3-甲基-4-羟基苯乙酸(14)、nodulisporipyrone A (15)、nodulisporipyrone B (16)、3,4-二甲氧基-乙酰苯乙醇(17).其中化合物1为新化合物,化合物2和3为新天然产物,新化合物的结构通过HRESIMS, 1D NMR和2DNMR等光谱技术确定.此外,对分离所得的化合物1～4进行了体外细胞毒活性测试,结果表明化合物3对SF-268、MCF-7、Hep G-2、A549有较强的细胞毒活性,其IC_(50)值分别为1.85、3.21、2.53、5.09mmol·L~(-1).     

3-取代卓酚酮5位偶联产物的溴氧化成环反应

报道了采用溴氧化3-异丙烯基卓酚酮和3-肉桂酰基卓酚酮合成杂环并卓酮化合物的新方法。3-异丙烯基卓酚酮5位偶联产物1a-1f和3-肉桂酰基卓酚酮5位偶联产物3a-3d分别在吡啶介质中与过量溴作用生成5-取代苯偶氮基-7-溴-3-甲基-8-氢环庚并呋喃-8-酮2a-2f和6-取代苯偶氮基-2-苯基-8-溴-4,9-二氢环庚并吡喃-4,9-二酮4a-4d。     

萘并呋喃类化合物的染料化光氧化及其杂环衍生物的合成与表征

萘并呋喃类化合物1、7在四苯基卟啉存在与氧低温反应给出相应的二氧杂环丁烷类产物2、8，室温下分别全部分解成乙酰基乙酰氧基化合物4、9。2和盐酸作用可给出呋喃3-位甲基及所在萘半环β位的二氯代产物6。4与盐酸反应通过失去萘α位的酰基，形成羟基呋喃化合物3，1在三溴化硼酸解下亦可得同一产物。4在醋酸钠/酸酐中环构生成3-乙酰基吡喃酮(5)。     

黑紫橐吾化学成分的分离与鉴定

利用各种色谱技术对黑紫橐吾的乙酸乙酯萃取部位进行分离纯化, 并且根据一维和二维波谱数据进行结构鉴定. 共分离得到4个呋喃雅槛蓝型倍半萜: 1α-氯-6β-异丁酰基-9-酮-10β-羟基-呋喃雅槛蓝烷(1), 1α-羟基-6β-异丁酰基-9-酮-10β-氢-呋喃雅槛蓝烷(2), 1α-羟基-6β-异丁酰基-9-酮-10α-氢-呋喃雅槛蓝烷(3)和1α,10β-二羟基-6β-当归酰基-9-酮-呋喃雅槛蓝烷(4). 其中化合物1为新化合物, 并且通过X射线单晶衍射确定了绝对构型; 化合物2~4为首次从该植物中分离得到.     

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.     

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.     

热裂解气相色谱-质谱法测定葡萄干提取物的热裂解产物

50g葡萄干用70%乙醇溶液300mL在80℃回流提取3h,提取两次,过滤提取物,滤液减压浓缩至干。残渣用5200裂解仪在400℃,500℃,600℃,800℃下处理,在各裂解温度下得到的裂解产物导入仪器进行气相色谱-质谱分析。结果表明:主要裂解产物是糠醛、呋喃甲醇、5-甲基糠醛、5-羟甲基-2-呋喃甲醛、2,3-二氢-3,5-二羟基-6-甲基-4H-吡喃酮,这些裂解产物是赋予卷烟具有独特香味和较好口感的重要物质。     

红树尖瓣海莲内生真菌Phomopsis longicolla HL-2232次级代谢产物研究

通过活性追踪的方法,从一株来源于药用红树尖瓣海莲的内生真菌Phomopsis longicolla HL-2232中分离鉴定了5个生物碱类化合物、1个色原酮类化合物以及4个甾醇类化合物,分别鉴定为:6-氨基嘌呤-9-羧酸甲酯(1),腺嘌呤核苷(2),尿嘧啶核苷(3),N,N'-二苯基尿素(4),(2S,2'R,3R,4E,8E,3'E)-2-(2'-羟基-3'-十八碳烯酰胺)-9-甲基-4,8-十八碳二烯-1,3-二醇(5),2-(2'S-羟丙基)-5-甲基-7-羟基对氧萘酮(6),fortisterol(7),(22E)-5α,8α-表二氧麦角甾-6,22-二烯-3β-醇(8),啤酒甾醇(9),β-谷甾醇亚油酸酯(10).其中化合物1为新化合物,化合物5为新天然产物,其碳谱数据至今未曾报道.细胞毒活性表明化合物1~3对肿瘤细胞A549,B16F10,HL-60,MCF-7具有不同程度的抑制活性.其中新化合物1对乳腺癌细胞(MCF-7)的IC50值为14.9μmol·L-1、化合物3对肺癌细胞(A549)的IC50值为8.6μmol·L-1,两者活性强于阳性对照药顺铂.     

一株昆虫内生真菌Alternaria sp.次级代谢产物研究

采用硅胶柱色谱,Sephadex LH-20凝胶柱色谱及HPLC等方法从昆虫共生真菌Alternaria sp.(Be-1)的发酵液分离得到7个代谢产物,经NMR,MS及理化性质等确定为4个环肽和3个聚酮类化合物,4-甲氧基格链孢酚(1),5'-methoxy-6-methyl-biphenyl-3,4,3'-triol(2),altenusin(3),二氢腾毒素(4),腾毒素(5),环(4-羟基-脯-亮)二肽(6)和cyclo(L-Phenylalanine-trans-4-hydroxy-L-proline)(7)。测定了化合物1-7对抗肿瘤治疗靶点-受体酪氨酸激酶的抑制活性,药理实验结果表明,化合物1-6对三种酪氨酸激酶(EGFR,VEGFR-1,c-Met)具有不同程度的抑制活性,化合物1,3,6对EGFR,VEGFR-1,c-Met均具有强的抑制作用,而且化合物6还有选择性抑制EGFR和c-Met的活性。     

红葱中的新化学成分

通过正相和反相硅胶柱色以及高效液相色谱,从红葱60%乙醇提取物中分离得到3个新化合物,利用物理化学和光谱学方法鉴定了其结构,分别为9,9'-二羟基-8,8'-二甲氧基-1,1'-二甲基-1H,1H-['4,4']双[萘并(2,3-c)呋喃]-3,3'-二酮(1),6,8-二羟基-3,4-二甲氧基-1-甲基-蒽醌-2-羧酸甲酯(2),2-乙酰基-3,6,8-三羟基-1-甲基蒽醌(3).这3个化合物均能不同程度地诱导稻瘟霉菌丝变形,其最小变形质量浓度(Mini-mummorphologicaldeformationmassconcentration,MMDC)分别为145.8,50.2和124.8μg/mL.利用MTT法测定了化合物抑制人类红白血细胞株K562细胞生长的活性,化合物2的IC₅₀为49.1μg/mL.     

Synthesis and cytotoxic activity of benzo[a]pyrano[3,2-h] and [2,3-i]xanthone analogues of psorospermine, acronycine, and benzo[a]acronycine

Condensation of 2-hydroxy-1-naphthalenecarboxylic acid with phloroglucinol afforded 9,11-dihydroxy-12H-benzo[a]xanthen-12-one (6). Construction of an additional dimethylpyran ring onto this skeleton, by alkylation with 3-chloro-3-methyl-1-butyne followed by Claisen rearrangement, gave access to 6-hydroxy-3,3-dimethyl-3H,7H-benzo[a]pyrano[3,2-h]xanthen-7-one (12) and 5-hydroxy-2,2-dimethyl-2H,6H-benzo[a]pyrano[2,3-i]xanthen-6-one (13), which were methylated into 6-methoxy-3,3-dimethyl-3H,7H-benzo[a]pyrano[3,2-h]xanthen-7-one (14) and 5-methoxy-2,2-dimethyl-2H,6H-benzo[a]pyrano[2,3-i]xanthen-6-one (15), respectively. Osmium tetroxide oxidation of 14 and 15 gave the corresponding (+/-)-cis-diols 16 and 17, which afforded the corresponding esters 18-21 upon acylation. Similarly, condensation of 2-hydroxy-1-naphthalenecarboxylic acid with 3,5-dimethoxyaniline gave 11-amino-9-methoxy-12H-benzo[a]xanthen-12-one (23) which was converted into 11-amino-9-hydroxy-12H-benzo[a]xanthen-12-one (24) upon treatment with hydrogen bromide in acetic acid. Alkylation with 3-chloro-3-methyl-1-butyne followed by Claisen rearrangement afforded 6-amino-3,3-dimethyl-3H,7H-benzo[a]pyrano[3,2-h]xanthen-7-one (25) and 5-amino-2,2-dimethyl-2H,6H-benzo[a]pyrano[2,3-i]xanthen-6-one (26). The new benzopyranoxanthone derivatives only displayed marginal antiproliferative activity when tested against L1210 and KB-3-1 cell lines. The only compounds found significantly active against L1210 cell line, 16 and 20, belong to the benzo[a]pyrano[3,2-h]xanthen-7-one series, which possess a pyran ring fused angularly onto the xanthone basic core.     

Benzofused tricycles based on 2-quinoxalinol

This paper describes our recent efforts to synthesize novel compound scaffolds integrating 2-quinoxalinol with privileged structures of 1,3-dihydro-benzoimidazol-2-one, 1,3-dihydro-benzoimidazole-2-thione, 3-hydroxy-1H-quinoxalin-2-one, 2H-benzo[1,4]oxazin-3-ol, 2H-benzo[1,4]thiazin-3-ol, and 1,3,4,5-tetrahydro-benzo[1,4]diazepin-2-one, respectively. Eight novel benzofused tricycles and their substituent diversity points were developed. These include pyrazino[2,3-g]quinoxaline-2,8-diol (I), 3-hydroxy-6,8,9,10-tetrahydro-1,4,6,10-tetraaza-cyclohepta[b]naphthalen-7-one (II), 6-hydroxy-4H-1-oxa-4,5,8-triaza-anthracen-3-one (III), 6-hydroxy-4H-1-thia-4,5,8-triaza-anthracen-3-one (IV), 6-hydroxy-1,1-dioxo-1,4-dihydro-2H-1lambda(6)-thia-4,5,8-triaza-anthracen-3-one (V), 6-hydroxy-1,3-dihydro-imidazo[4,5-g]quinoxalin-2-one (VI), 6-hydroxy-1,3-dihydro-imidazo[4,5-g]quinoxaline-2-thione (VII), and 7-hydroxy-1,4-dihydro-pyrazino[2,3-g]quinoxaline-2,3-dione (VIII). This strategy of integrating two benzofused privileged structures into one molecule may provide a greater chance for the discovery of novel lead compounds.     

Isolation and Identification of Secondary Metabolites Produced by Phytopathogenic Fungus Corynespora cassiicola from Hevea brasiliensis

The secondary metabolites of the phytopathogenic fungus Corynespora cassiicola CC01 from Hevea brasiliensis were investigated. As a result, two new compounds, 5-acetyl-7-hydroxy-6- methoxybenzofuran-2(3H)-one (1) and (S)-2-(2,3-dihydrofuro [3,2-c]pyridin-2-yl)propan-2-ol (2), together with seven known compounds, 4,6,8-trihydroxy-3,4-dihydronaphthalen-1(2H)-one (3), 3,6,8-trihydroxy-3,4-dihydronaphthalen-1(2H)-one (4), curvulin acid (5), 2-methyl-5-carboxymethyl- 7-hydroxychromone (6), tyrosol (7), p-hydroxybenzoic acid (8) and cerevisterol (9), were isolated from the fermentation extract by comprehensive silica gel, reverse phase silica gel, Sephadex-LH20 column chromatography and high-performance liquid chromatography (HPLC). The structures of these compounds were identified by using high-resolution electrospray mass spectrometry (HRESIMS), nuclear magnetic resonance spectroscopy (NMR), optical rotation, ultraviolet and infrared spectroscopy techniques and a comparison of NMR data with those reported in the literature. Compounds 1 and 2 were new compounds, and compounds 3–9 were discovered from this phytopathogenic fungus for the first time. Compounds 1–9 were tested for phytotoxicity against the fresh tender leaf of Hevea brasiliensis, and the results show that none of them were phytotoxic. Additionally, these compounds were subjected to an antimicrobial assay against three bacteria (E. coli, methicillin-resistant Staphylococcus aureus and Micrococcus luteus), but they showed no activity.     

Five new peltogynoids from underground parts of Iris bungei: a Mongolian medicinal plant

Five new peltogynoids, irisoids A-E (1-5), have been isolated from the underground parts of Iris bungei. The structures of the new compounds were established on the basis of spectroscopic methods and were found to be 1,8,10-trihydroxy-9-methoxy-[1]benzopyrano-[3,2-c][2]-benzopyran-7(5H)-one (1), 1,8-dihydroxy-9,10-dimethoxy-[1]benzopyrano-[3,2-c][2]-benzopyran-7(5H)-one (2), 1,10-dihydroxy-8,9-dimethoxy-[1]benzopyrano-13,2-c][2]-benzopyran-7(5H)-one (3), 1,8-dihydroxy-9,10-methylenedioxy-[1]benzopyrano-[3,2-c][2]-benzopyran-7(5H)-one (4), and 1,8,11-trihydroxy-9,10-methylenedioxy-[1]benzopyrano-[3,2-c][2]-benzopyran-7(5H)-one (5). The structure of irisoid B (2) was established unambiguously by X-ray diffraction study.     

Alpha-glucosidase inhibitory constituents from Cuscuta reflexa

Two new compounds, 7'-(3',4'-dihydroxyphenyl)-N-[(4-methoxyphenyl)ethyl]propenamide (4), and 7'-(4'-hydroxy,3'-methoxyphenyl)-N-[(4-butylphenyl)ethyl]propenamide (5) have been isolated from Cuscuta reflexa along with five known compounds, 6,7-dimethoxy-2H-1-benzopyran-2-one (1), 3-(3,4-dihydroxyphenyl)-2-propen-1-ethanoate (2), 6,7,8-trimethoxy-2H-1-benzopyran-2-one (3), 3-(4-O-beta-D-glucopyranoside-3,5-dimethoxyphenyl)-2-propen-1-ol (6), 2-(3-hydroxy-4-methoxyphenyl)-3,5-dihydroxy-7-O-beta-D-glucopyranoside-4H-1-benzopyrane-4-one (7), reported for the first time from this species. Structures of these compounds were determined by spectral analysis. These compounds showed strong inhibitory activity against alpha-glucosidase.     

Synthesis and antimicrobial activity of some derivatives of (7-hydroxy-2-oxo-2H-chromen-4-yl)-acetic acid hydrazide

(7-Hydroxy-2-oxo-2H-chromen-4-yl)-acetic acid hydrazide (2) was prepared from (7-hydroxy-2-oxo-2H-chromen-4-yl)-acetic acid ethyl ester (1) and 100% hydrazine hydrate. Compound 2, is the key intermediate for the synthesis of several series of new compounds such as Schiff's bases 3a-l, formic acid N'-[2-(7-hydroxy-2-oxo-2H- chromen-4-yl)acetyl] hydrazide (4), acetic acid N'-[2-(7-hydroxy-2-oxo-2H-chromen-4- yl)-acetyl] hydrazide (5), (7-hydroxy-2-oxo-2H-chromen-4-yl)-acetic acid N'-[2-(4- hydroxy-2-oxo-2H-chromen-3-yl)-2-oxoethyl] hydrazide (6), 4-phenyl-1-(7-hydroxy-2- oxo-2H-chromen- 4-acetyl) thiosemicarbazide (7), ethyl 3-{2-[2-(7-hydroxy-2-oxo-2H- chromen-4-yl)-acetyl]hydrazono}butanoate (8), (7-hydroxy-2-oxo-2H-chromen-4-yl)- acetic acid N'-[(4-trifluoromethylphenylimino)methyl] hydrazide (9) and (7-hydroxy-2- oxo-2H-chromen-4-yl)acetic acid N'-[(2,3,4-trifluorophenylimino)-methyl] hydrazide (10). Cyclo- condensation of compound 2 with pentane-2,4-dione gave 4-[2-(3,5- dimethyl-1H-pyrazol-1-yl)-2-oxoethyl]-7-hydroxy-2H-chromen-2-one (11), while with carbon disulfide it afforded 7-hydroxy-4-[(5-mercapto-1,3,4-oxadiazol-2-yl)methyl]-2H- chromen-2-one (12) and with potassium isothiocyanate it gave 7-hydroxy-4-[(5- mercapto-4H-1,2,4-triazol-3-yl)methyl]-2H-chromen-2-one (14). Compound 7 was cyclized to afford 2-(7-hydroxy-2-oxo-2H-chromen-4-yl)-N -(4-oxo-2-phenylimino- thiazolidin-3-yl) acetamide (15).     

Isolation and structure determination of two new constituents from the fruits of Morinda citrifolia Linn

Studies on the chemical constituents of the fruits of Morinda citrifolia Linn. have led to the isolation of two new compounds, morinaphthalene (=1,3,6,7-tetrahydroxy-2-hydroxymethyl-1,2,3,4-tetrahydronaphthalene, (1); and morindafurone (=5-hydroxy-1,10b-dihydro-6H-anthra [1,9-bc] furan-6-one, (2); as well as two known constituents, 1,8-dihydroxy-6-methoxy-3-methyl-9-anthrone (3) and 2,4-dimethoxy-9-anthrone (4). Their structures were elucidated by spectral analysis including 2D NMR techniques.     

New Monoterpene-Substituted Dihydrochalcones from Piper aduncum

Five New unusual monoterpene-substituted dihydrochalcones, the adunctins A–E (1″S)-1-{2′-hydroxy-4′-methoxy-6′-[4″-methyl-1″-(1?-methylethyl)cyclohex-3″ -en-1″ -yloxy]phenyl}-3-phenylpropan-1-one ( 1 ), (5aR*,8R*,9aR*)-3-phenyl-1-[5′,8′,9′,9′a-tetrahydro-3′-hydroxy-1′-methoxy-8′-(1″-methylethyl)-5′-a-methyldibenzo-[b,d]furan-4′-yl]propan-1-one ( 2 ), (2′R*,4″S*)-1-{6′-hydroxy-4′-methoxy-4″-(1?-methylethyl)spiro[benzo[b]-furan-2′(3′H),1″ -cyclohex-2″ -en]-7′-yl}-3-phenylpropan-1-one ( 3 ), (2′R*,4″R*)-1-{6′-hydroxy-4′-methylethyl-4″-(1?-methylethyl)spiro[benzo[b]furan-2′(3′H),1″-cyclohex-2″-en]-7′-yl}-3-phenypropan-1-one ( 4 ), and (5′aR*,6′S*, 9′R*,9′aS*)-1-[5′a,6′,7′,8′,9′a-hexahydro-3′,6′-methoxy-6′-methyl-9′-(1″-methylethyl)dibenzo[b,d]-furan-4′-yl]-3-phenylpropan-1-one ( 5 ) were isolated from the leaves of Piper aduncum (Piperaceae) by preparative liquid chromatography. In addition, (?)-methyllindaretin ( 6 ), trans-phytol, and α-tocopherol ( = vitamin E) were also isolated and identified. The structures were elucidated by spectroscopic methods, including 1D- and 2D-NMR spectroscopy as well as single-crystal X-ray diffraction analysis. The antibacterial and cytotoxic potentials of the isolates were also investigated.     

A new homostilbene and two new homoisoflavones from the bulbs of Scilla scilloides

A new homostilbene, named scillabene A (2), and two new homoisoflavones, named scillavones A (3) and B (4), were isolated from the bulbs of Scilla scilloides DRUCE (Liliaceae) along with 13 known compounds comprising a homostilbene, seven homoisoflavones, a xanthone, a lignan, and three nortriterpenes. The structures of 2-4 were characterized as 3,5,4'-trihydroxy-3'-methoxy-4-methyl-trans-stilbene, (3R)-5,7,2'-trihydroxy-3',4'-dimethoxyspiro{2H-1-benzopyran-7'-bicyclo[4,2,0]octa[1,3,5]-trien}-4-one and (3S)-3-(3,4-dihydroxybenzyl)-5-hydroxy-6,7-dimethoxychroman-4-one, respectively, on the basis of spectroscopic data and X-ray crystallographic analysis.     

Secondary metabolites from fungus Alternaria sp. CIB 108

A new compound,3-butyryl-6-[rel-(1S,2S)-1,2-dihydroxypropyl]-4-hydroxy-2H-pyran-2-one(1),was isolated from the solid fermented rice culture of Alternaria sp.CIB 108,along with three known ones,deoxyradicinin(2),3-epiradicinol(3),and 3- epideoxyradicinol(4).Their structures were elucidated on the basis of spectroscopic data.The single crystal X-ray diffraction was applied to further clarify the structure of 1.Furthermore,compounds 1-4 possessed no cytotoxicity against several cell lines(HeLa, HepG2,and Ros) and showed no antibacterial activity at 40μmol/L.