南海针小月柳珊瑚化学成分的研究

南海针小月柳珊瑚化学成分的研究邓松之＊李凤英彭胜石饶志刚吴厚铭徐竞辉（中国科学院广州化学研究所广州５１０６５０）（中国科学院上海有机化学研究所上海）关键词柳珊瑚，化学成分，提取分离，结构１９９６－１２－１６收稿，１９９７－０６－１０修回中国科学院“八...     

南海柳珊瑚Menella Spinifera Kukenthal化学成分的研究(一)

从中国南海针小月柳珊瑚(Menella Spinifera Kukenthal)中分离到一种长链甘油醚,其结构经UV、IR、MS、~1H NMR、~(13)C NMR、~1H-~1H COSY以及元素分析确定为3—十八烷氧基—1,2—丙二醇鲨肝醇(Ⅰ)。本文是第一次报导它存在于该种属柳珊瑚之中。 (Ⅰ)的化学结构     

南海柳珊瑚Menella Spinifera Kukenthal化学成分的研究(二)

从中国南海针小月柳珊瑚（MenellaSpiniferaKukenthal）中分离到一种内盐，其结构经UV、IR、MS、1HNMR和13CNMR分析确定为：N-甲基吡啶羧酸内按盐。本文是首次报导这个化合物的波谱数据。     

中国南海珊瑚化学研究新进展

本文综述了近年来中国南海珊瑚代谢产物中一些新的或有生理活住的物质，其中包括萜类、甾醇及含氮化合物等。     

中国南海矮小短指软珊瑚(Sinularia nanolobata)的化学成分研究

运用硅胶柱色谱、凝胶柱色谱和高效液相色谱等分离技术,对中国南海西瑁岛矮小短指软珊瑚的丙酮提取物中的化学成分进行了系统研究,从中分离得到10个化合物,并采用多种波谱技术确定了这些化合物的化学结构.分别鉴定为罗伯塔特(1)、(17R)-loba-8,10,13(15)-triene-17,18-diol(2)、α-生育醌(3)、(1E,3Z,7E,11R,12R)-11-羟基-12-甲氧基-1-异丙基-4,8,12-三甲基-环十四碳-1,3,7-三烯(4)、(+)-(1E,3E,7E,11R,12S)-11,12-epoxy-11,12-dihydrocembrene-C(5)、(1E,3E,7R,8S,11E)-7,8-环氧-1-异丙基-4,8,12-三甲基-环十四碳-1,3,11-三烯(6)、24-亚甲基-胆固醇(7)、孕烯醇酮(8)、3β,6α,11-三羟基-24-亚甲基-9,11-断-5α-胆甾-7-烯-9-酮(9), Sinugrandisterol A (10).其中化合物1为新的异戊烯基榄烷型二萜化合物.生物活性实验结果表明,化合物3对蛋白酪氨酸磷酸酶1B (PTP1B)的酶...     

中国南海裸鳃目软体动物美丽拟皮片鳃(Dermatobranchus orna-tus)及其可能的食源动物柳珊瑚Muricella sp.的化学成分研究

从中国南海的裸鳃目软体动物美丽拟皮片鳃(Dermatobranchus ornatus)中分离得到4个eunicellane型二萜: Ophirin (1), calicophirin B (2), 13-去乙酰氧基 calicophirin B (3)及3-去乙酰基-13-去乙酰氧基calicophirin B (4); 而由同时、同地采集到的柳珊瑚Muricella sp. 中则分离得到calicophirin B (2), 13-去乙酰氧基 calicophirin B (3), astrogorgin (5) 及类似物6. 这些化合物的结构经波谱学实验并与文献报道的数据相对照得以确定, 并首次对Ophirin (1) 的NMR数据进行了全归属. Ophirin (1) 的单晶X衍射实验不但进一步确证了化合物的结构, 而且使这一类化合物的立体结构表述得到修正. 本文是对Dermatobranchus属软体动物化学成分研究的首次报道; 研究提示, 美丽拟皮片鳃能通过选择适当的食物, 并将食物中有用的次生代谢产物转移、富集到身体的特定部位, 使之成为自身的化学防性物质. 美丽拟皮片鳃与Muricella 属柳珊瑚中共同出现的类似化合物支持二者间可能存在的捕食与被捕食的生态学关系.     

南海石珊瑚Pavona frondifera Dana化学成分的研究

从中国南海石珊瑚（PavonafrondiferaDana）中分离到两个化合物。经紫外（UV）、红外（IR）、核磁共振（1~HNMR，（13）~CNMR）、质谱（EIMS．HRMS）等波谱分析，确定其结构为：3－甲基－6－氨基嘌呤和胆甾醇。     

南海佳丽鹿角珊瑚化学成分的研究(一)

从中国南海的一种石珊瑚一佳丽鹿角珊瑚（Acroporapuchro）的乙酸乙酯可溶部分获得两个有机化合物：正十六碳酸（Ⅰ）和（24S）－24-甲基胆甾醇（Ⅱ）。它们的结构是通过EIMS、IR、1HNMR、13CNMR和DEPT等实验分析确定的。其中纯的（24S）-24-甲基胆甾醇是首次从自然界大量获得。本文首次提供化合物（Ⅱ）的完整波谱数据。     

中国南海软珊瑚Scleronephthya sp.化学成分的研究

对中国南海的软珊瑚Scleronephthya sp.的化学成分进行研究,从有免疫调节活性的乙醚可溶物中分离鉴定了13个化合物,经1H NMR,13C NMR,HMQC,HMBC,1H-1H COSY和MS等光谱分析并结合文献数据,确证其结构分别为:3β-羟基-20-烯孕甾烷乙酸酯(1),3β-羟基-5,20-二烯孕甾烷乙酸酯(2),3-酮-20-烯孕甾烷(3),1,2-环氧-3-酮-20-烯孕甾烷(4),1,20-二烯-3-酮孕甾烷(5),1-烯-3-酮-20S-甲基-21-羟基孕甾烷乙酸酯(6),1-烯-3-酮-20β-羟基孕甾烷乙酸酯(7),1-烯-3,22-二酮胆甾烷(8),1,24-二烯-3-酮-22,23-二羟基胆甾烷(9),O-methylisogrifolin(10),(1R,3S,4S,7E,11E)-3α,4α-环氧-7,11,15-三烯西松烷(11),玉米黄素12和6-溴-3-羧酸吲哚(13),其中化合物4,6和10是首次从自然界分离得到.首次对化合物6,7和10的波谱数据进行了报道,而且利用2D NMR对其进行了全归属.对化合物1～7可能的生源关系也进行了探讨.化合物6和7对人宫颈癌细胞(HELA)有抑制活性,IC50分别为3.3和6.3 mol/L;化合物7对肝癌细胞(BE7402)和人白血病细胞(HL-60)也显示抑制活性,IC50分别为3.1和0.26mol/L;化合物11对COX-2显示强烈的抑制活性,IC50为0.455 mol/L.     

南海软珊瑚Sarcophyton molle化学成分的研究

从中国南海软肉芝软珊瑚(Sarcophyton molle)中分离到七个化合物, 经紫外光谱(UV), 红外光谱(IR), 质谱(MS)和核磁共振光谱(1H NMR, 13C NMR)分析, 确定了其化学结构。它们是: 异新西松烯(1), (E, E, E)-7, 8-环氧-1-异丙基-4, 8, 12-三甲基-十四环-1,3, 11-三烯(2), 正十八烷酸(3), 鲨肝醇(4), 神经酰胺(5), 胸腺嘧啶(6), 胸腺嘧啶脱氧核苷(7)。其中化合物(2)为新化合物。本文是第一次报道软珊瑚Sarcophyton molle的化学成分。     

Three New Polyoxygenated Steroids from Two Species of the South China Sea Gorgonian Muricella flexuosa and Menella verrucosa Brundin

Three new polyoxygenated steroids, muricesteroid ( 1 ), and menellsteroids A ( 2 ) and B ( 3 ), were isolated from two species of the South China Sea gorgonian Muricella flexuosa and Menella verrucosa Brundin , respectively. The structures of these new compounds were elucidated on the basis of extensive spectroscopic analysis, chemical methods and comparison with known related compounds.     

Two new eunicellin diterpenoids from the South China Sea gorgonian Muricella sibogae and their bioactivities

A systematic re-study on gorgonian Muricella sibogae from South China Sea yielded 10 eunicellin-based diterpenoids including two new ones, sibogins C and D (1 and 2). Their structures were elucidated by extensive spectroscopic analyses (1D and 2D NMR, IR and MS) and by comparison with data reported in literatures. All the isolates were tested for cytotoxic and antifouling activities. Compounds 3 and 5 showed significant antifouling activity against the green mussel Perna viridis, and especially 3 was suggested as a potent low-toxic antifouling agent with a large LC₅₀/EC₅₀ value of 18.6. This was the first report on the antifouling activity of the eunicellin-type diterpenoids against the green mussel.     

New Eunicellin Diterpenes and 9,10‐Secosteroids from the Gorgonian Muricella sibogae

Bioactivity‐guided isolation of the rare gorgonian Muricella sibogae (Nutting ) yielded the two new eunicellin diterpenes sibogin A and B ( 1 and 2 ), the three new 9,10‐secosteroids sibogol A–C ( 6 – 8 ), together with the three known eunicellin diterpenes 3 – 5 and the five known 9,10‐secosteroids 9 – 13 . Their structures were established by extensive spectral analysis (1D‐ and 2D‐NMR, IR, and MS). The cytotoxicity of the isolates 1 – 13 was evaluated in vitro against the selected tumor cell lines P388 and BEL‐7402. All the compounds showed only weak activity against P388 cell lines, with an inhibition rate ranging from 10 to 60% at a concentration of 50 μg/ml, whereas the were inactive against BEL‐7402 cell lines.     

Chemical constituents of the Gorgonian Dichotella fragilis (Ridleg) from the South China Sea

Two new steroidal glycosides, fragilioside A (1) and fragilioside B (2), along with five known compounds (3-7) were isolated from the gorgonian Dichotella fragilis (Ridleg) collected from the South China Sea. The structures of the new compounds (1 and 2) were elucidated by comprehensive analysis of spectral data, especially 2D NMR. The brine shrimp lethality and antifouling activity of the isolated compounds were also evaluated.     

New Briaranes from the South China Sea Gorgonian Junceella fragilis

Three new briarane diterpenes, junceellonoids C–E ( 1 – 3 ), along with six known briaranes, junceellin A ( 4 ), praelolide ( 5 ), and junceellolides A‐D ( 6 – 9 ), were isolated from the EtOH/CH₂Cl₂ extracts of the South China Sea gorgonian coral Junceella fragilis. The structures of 1 – 3 were established by extensive spectroscopic analysis, including 1D‐ and 2D‐NMR data. Compounds 1 and 2 exhibited mild cytotoxicity against human galactophore carcinoma (MDA‐mB‐231 and MCF‐7) cells at the concentration of 100 μM .     

Polyhydroxylated Sterols from the South China Sea Gorgonian Verrucella umbraculum

Two new polyhydroxylated sterols, named verumbsteroids A and B ( 1 and 2 , resp.), along with seven known analog, 3 – 9 , were isolated from the gorgonian Verrucella umbraculum collected from the South China Sea. The structures and relative configurations of the new compounds were elucidated by comprehensive spectroscopic investigations. The absolute configuration of 1 was determined by using modified Mosher method with the acetonide derivative of 1 . Compounds 1 and 3 – 5 were found to show cytotoxicities against five human tumor cell lines (HL‐60, K562, HeLa, A‐549, and HCT‐116) with the IC₅₀ values ranging from 2.76 to 9.62 μM .     

Polyhydroxylated Steroids from the South China Sea Gorgonian Anthogorgia sp.

Four new polyhydroxylated steroids, namely anthogorgsteroids A–D ( 1 – 4 ), were isolated from the South China Sea gorgonian Anthogorgia sp. The structures of these compounds were elucidated by detailed spectroscopic analyses and comparison with reported data.     

A new briarane-type diterpenoid from the South China Sea Gorgonian Dichotella gemmacea

One new briarane-type diterpenoid, dichotellide V (1), along with four known analogues, gemmacolide N (2), dichotellide J (3), junceelin A (4) and junceellolide A (5), was isolated from the South China Sea gorgonian Dichotella gemmacea. All of the isolated compounds (1–5) were established by comprehensive analysis of the spectral data, especially 1D and 2D NMR (HMQC and HMBC) spectra. The cytotoxic activities of these compounds were evaluated.