3αβ-羟基-4α-氯-7αβ-甲基六氢茚-1,5-二酮和4αβ,5β-环氧-8αβ-甲基十氢萘-1,6-二酮的晶体结构和分子构型

用X射线晶体结构分析法测定了氯代羟基六氢茚二酮(1)和环氧十氢萘二酮(2)的晶体结构和分子构型.化合物1属正交晶系,空间群为Pbca,晶胞参数α=10.439(1),b=19.950(2),c=9.455(1)A,Z=8;化合物2属单斜晶系,空间群为P2_1/c,晶胞参数α=8.355(2),b=9.221(2),c=25.801(4)A,β=294.19(1)°,Z=8.在RASA-IIS型四圆衍射仪上收集了这两个化合物的衍射数据,用直接法解晶体结构,经块对角矩阵最小二乘修正,对化合物1的1810个独立的可观察反射,R=0.043;对化合物2的1804个独立的可观察反射,R=0.064.化合物l带有α-Cl,β-CH_3和β-OH.由此推断环氧六氢茚二酮(3)的分子构型带有β-CH_3和β-环氧.化合物2中的甲基和环氧基均为β构型,与3相似.因此Danishefsky等由核磁共振所推断的关于2的分子构型中的α环氧应校正为β环氧.     

Beauveria feline培养物中的新的cyclodepsipeptide类化合物

从微生物(Beauveria felina)的发酵液的乙酸乙酯萃取物中分离得到8个结构新颖的cyclodepsipeptide类化合物,经光谱(尤其是1D、2D NMR及MS)及化学方法鉴定了所有的8个化合物的结构,结果表明1-5为新的化合物,命名为felinains A-E,3个已知化合物分别鉴定为Antibiotic M6124,isarin及roseocardin.通过手性HPLC技术对化合物水解所得氨基酸构型的测定,确定了5个新化合物的绝对构型,并对所有化合物进行了生物学活性测试.     

水杨酸类糖酯化合物的合成及其生物活性

将水杨酸及乙酰水杨酸分别与溴代糖作用, 合成了10个水杨酸类糖酯化合物. 所有化合物经元素分析和1H NMR确认了其结构, 并证明产物为β-构型, 反应具有立体专一性. 生物活性初步测定结果表明, 该类化合物具有一定的诱导活性, 且一些化合物的诱导活性好于水杨酸.     

具有细胞毒性的两种四羟基甾醇化合物的分离与结构

报道南海湛江硇洲岛软珊瑚Dendronephthya sp.中两种具有细胞毒性的四羟基甾醇化合物:23-降-24-亚甲基-麦角甾-3β,5α,6β,7β-四醇(1)和24-亚甲基-麦角甾-3β,6β,9α,19β-四醇(2),其结构通过波谱和化学方法确定,其中化合物1为新化合物,化合物2首次从该属珊瑚中获得.化合物1对肿瘤细胞BEL-7402,MCG,MCF,LOVO和HepG-2具有抑制作用,其IC50值分别为32.2,20.5,2.0,5.5和18.6μg/mL;化合物2对肿瘤细胞MCG和LOVO作用的IC50值分别为22.0和和13.8μg/mL.     

3aβ-羟基-4α-氯-7αβ-甲基六氢茚-1,5-二酮和4aβ,5β-环氧-8aβ-甲基十氢萘1,6-二酮的晶体结构和分子构型

用X射线晶体结构分析法测定了氯代羟基六氢茚二酮(1)和环氧十氢萘二酮(2)的晶体结构和分子构型。化合物1属正交晶系,空间群为Pbca,晶胞参数a=10.439(1),b=19.950(2),c=9.455(1)A,Z=8;化合物2属单斜晶系,空间群为P2~1/c,晶胞参数a=8.355(2),b=9.221(2),c=25.801(4)A,β=94.19(1)`,Z=8。在RASA-IIS型四圆衍射仪上收集了这两个化合物的衍射数据,用直接法解晶体结构,经块对角矩阵最小二乘修正,对化合物1的1810个独立的可观察反射,R=0.043;对化合物2的1804个独立的可观察反射,R=0.064。化合物1带有a-Cl,β-CH~3和β-OH。由此推断环氧六氢茚二酮(3)的分子构型带有β-CH~3和β-环氧。化合物2中的甲基和环氧基均为β构型,与3相似,因此Danishefsky等由核磁共振所推断的关于2的分子构型中的α环氧应校正为β环氧。     

茅苍术根茎中的两个新化合物

运用多种柱色谱技术对茅苍术根茎进行了系统的化学成分研究,从其80%乙醇提取物中分离得到一个新的4,6-二炔烯类化合物和一个新的香豆素类化合物,分别命名为(10R,11R,12R)-十三烷-2E,8E-二烯-4,6-二炔-1,10,11,12,13-五醇-10-O-β-D-吡喃葡萄糖苷(1)和isoscopoletin 6-O-α-L-吡喃鼠李糖基-(1→6)-β-D-吡喃葡萄糖苷(2).其平面结构通过UV,IR,HR-ESIMS,1D和2D NMR等谱学技术确定.化合物1的相对构型通过纽曼投影式分析优势构象并结合1D NOESY的方法确定,而绝对构型通过比较电子圆二色谱(ECD)的方法确定.相关结果为链状多元醇的立体构型研究提供了参考.在10μmol·L~(-1)浓度下,化合物1和2对α-葡萄糖苷酶及蛋白酪氨酸磷酸酶1B表现出弱的抑制活性.     

川桂皮中具有免疫调节活性的甾体和苯丙素类化学成分

对川桂Cinnamomum wilsonii皮的化学成分进行了研究,从中分离并鉴定出1个新的甾体类化合物,(3S,22R,24R)-stigmast-5-ene-3β,22α-diol(1),和10个已知化合物,stigmast-5-ene-3β,7α,22α-triol(2),24-ethylcholest-5-ene-3β,4β,22α-triol(3),stigmast-5-ene-3β,7α-diol(4),β-谷甾醇(5),β-胡萝卜苷(6),(1R,2R)-1-(4-hydroxy-3-methoxyphenyl)-1,2,3-propanetriol(7),(1S,2S)-1-(4-hydroxy-3-methoxyphenyl)-1,2,3-propanetriol(8),丁子香酚(9),甲氧基丁子香酚(10)和methyl(E)-ferulate(11).通过波谱分析和Cu靶单晶X射线衍射方法确定了新化合物1的结构及其绝对构型.测试了化合物1～11的体外免疫调节活性,1,5和6能显著抑制刀豆A诱导的小鼠T细胞增殖,6和9能显著抑制脂多糖诱导的小鼠B细胞增殖.     

N-杂环卡宾Ru配合物的合成及其在Suzuki偶联反应中的催化应用

合成了两个新的氮杂环卡宾金属钌配合物1和2,通过核磁共振氢谱、核磁共振碳谱、红外光谱和元素分析对其结构进行了表征,同时,X射线单晶衍射确证了配合物2的结构为cis(I)顺式构型.化合物1和2均能在温和的反应条件下有效催化卤代芳烃和苯硼酸的Suzuki偶联反应,并表现出较高的催化活性.     

(Z)-1-三苯基锡基-3-对氯苯基-1-丁烯-3-醇及其卤代物的合成、表征和晶体结构

在氮气保护下,3-对氯苯基-1-丁炔-3-醇与三苯基氢化锡进行游离基加成反应,获得加成物(Z)-1-三苯基锡基-3-对氯苯基-1-丁烯-3-醇(1).加成物(1)与卤素反应后,与锡原子相连的苯基被取代,得到一卤代、二卤代和混合二卤代物(2-8).通过元素分析、¹HNMR和IR表征了化合物1～8的结构,并测定了加成物(1)、一溴代物(3)和二溴代物(5)的晶体结构.在加成物(1)的晶体结构中存在一对对映体,由于分子内存在较弱的O→Sn配位作用,构成以锡原子为中心的扭曲四面体构型.在化合物3和5分子中,存在分子内O→Sn配位键,构成以锡为中心的扭曲三角双锥构型.该系列化合物分子内的O→Sn配位能力和Lewis酸性强弱的顺序为:二卤化物>一卤化物>加成物;氯代物>溴代物>碘代物.     

Co_3(CO)_9(μ_3-PR)、Co_4(μ-CO)_2(CO)_8(μ_4-PR)_2和Co_2Fe(CO)_9(μ_3-PR)原子簇化合物合成与结构

本文合成了数个以有机磷作桥基配位体的同核钴和异核铁钴原子簇羰基化合物.通过元素分析、IR谱和~1H-NMR谱测定,确定三核钴簇合物Co_5(CO)_9-(μ_3-PR)和异核铁钴簇合物Co_2Fe(CO)_9(μ_3-PR)的分子骨架Co_3P和Co_2FeP具有三角锥构型,而四核钴簇合物Co_4(μ-CO)_2(CO)_8(μ_4-PR)_2的分子骨架Co_4P_2为八面体构型.     

云南美登木内生真菌Phomopsis sp. Lz42的化学成分

从云南美登木内生真菌Phomopsis species Lz42的琼脂平板发酵物中分离得到2个倍半萜和5个麦角甾醇类化合物(1~7), 其中化合物1和2为新化合物. 应用波谱技术确定其结构为4-Deacetyl-10-oxo-dihydrobotrydial(1)和麦角甾-6,22-二烯-5α,8α-环二氧-3-甲酸酯(2).     

Steroid compounds of marine sponges. VII. Preparation of derivatives of sokotrasterol and halistanol sulfates and structure-activity interrelationships among these compounds

Five new sulfated derivatives of sokotrasterol and halistanol have been obtained: 24-nor-5α-cholane-2β,3α,6α,23-tetraol 2β,3α,6α-tri(sodium sulfate); 24-nor-5α-cholane-2β,3α,6α,23-tetraol 2β,3α,6α-tri(sodium sulfate) 23-palmitate; 24ε,25-dimethyl-5α-cholestane-2β,3α,6α-triol 3α-(sodium sulfate); 24ε,25-dimethyl-5α-cholestane-2β,3α,6α-triol 6α-(sodium sulfate); and 24ε,25-dimethyl-5α-cholestane-2β,3α,6α-triol 2β,6α-di(sodium sulfate). The inhibiting and membranolytic properties of the polysulfated steroids from sponges and their derivatives have been studied. It has been shown that physiological activity in this series of compounds depends on biphilicity.     

Triterpene glycosides of Astragalus and their genins XLIV. Structure of cyclocarposides A and C

The structures of two new cycloartane glycosides — cyclocarposides A and C, isolated from the herbAstragalus coluteocarpus Boiss. — have been established on the basis of spectral characteristics and chemical transformations. Cyclocarposides A and C are: 204R,24S-epoxycycloartane-3β,6α,17β,25-tetraol 3-O-(2-O-acetyl-β-D-xylopyranoside)6-O-(2-O-acetyl-α-L-rhamnopyranoside) and 20R,24S-epoxycyloartane-3β,6α,16β,25-tetraol 3-O-(2-O-acetyl-β-D-xylopyranoside) 6-O-α-L-rhamnopyranoside, respectively.     

匐枝马尾藻的化学成分研究

首次报道从中国北海匐枝马尾藻Sargassum polycystcum分离得到3个纯化合物 ，经过MS，IR，~1H NMR，~(13)C NMR（DEPT），HMQC和HMBC等波谱技术鉴定为： 豆甾-3β-羟基-5，23，25-三烯(1)，3-二下五烷氧基-1，2-丙二醇(2)，24ξ-甲 基胆甾-3β，5α，6β，25-四醇-25-乙酸酯(3)，其中化合物1为新化合物。     

The Identification of Two New Sterols from Marine Organism

Marineorganismsproducedmanyinterestingphannacologicallyandbiologicallyactiviemetabolitessuchasantibacterium,anticancerandantimicrobialactivecompounds'-'.lnrecentyears,avarietyofsterolshavebeenreportedfrommarineinvertebratesandsponges'-'.Moreandmorechemistsandbiologistspayattentiontotheconstituentsofspongesandcorals.ThirteencompoundshavebeenisolatedfromthespongePolymastiasobustiaandeightycompoundshavebeenobtainedfromthesoftcoralSinulariainexPlicita.InthispaPerwewou1dliketoreportthestructurale…     

Studies on the Constituents of Ganoderma Lucidum

The methanolic extract of fruit bodies of cultivated Ganoderma lucidum was separated by silica gel column chromatography and preparative thin-layer chromatography to give ten compounds. On the basis of spectral analysis, chemical procedures and gas chromatography, d-mannitol (1), ergosta-7, 22-dien-3β-yl palmitate (2), ergosterol (3), ergosta-7, 22-dien-3β-ol (4), 5α-lanosta-7,9(11),24-trien-3β,26-diol (5), ergosterol peroxide (6), 24,25,26-trihydroxy-5α-lanosta-7,9(11)-dien-3-one (7), 5α-lanosta-7,9(11)-dien-3β,24,25,26-tetraol (8) and 8,9-epoxyergosta-5,22-dien-3β,15-diol (9) were identified. Among these compounds, 8,9-epoxyergosta-5,22-dien-3β,15-diol was first separated from Ganoderma lucidum.     

Steroids of the spirostan and furostan series from Nolina microcarpa I. Structures of nolinospiroside C and nolinofurosides A and C

In addition to the know steroid sapogenin (25S)-ruscogenin (I), three new glycosides have been isolated from the leaves ofNolina microcarpa S. Wats. (family Dracaenacea), and the following structures are suggested for them: (25S)-spirost-5-ene-1β,3β-diol 1-O-β-D-fucopyranoside (nolinospiroside C, II), (25S)-furost-5-ene-1β,3β,22α,26-tetraol 1-O-β-D-fucopyranoside (nolinofuroside A, III), and (25S)-furost-5-ene-1β, 3β, 22α, 26-tetraol 1-O-β-D-fucopyranoside 26-O-β-D-glucopyranoside (nolinofuroside C, V).     

Two new steroidal glucosides from Ophiopogon.japonicus （L.f.） Ker-Gawl

Two new steroidal glucosides, 26-O-β-D-glucopyranosyl （25S）-furost-5-ene-1β,3β,22α,26-tetraol l-O-β-D-xylopyranosyl- （1 → 3）-[α-h-rhamnopyranosyl-（1 → 2）]-[β-D-fueopyranoside and （25R） spirost-5-ene-3β,14α-diol-3-β-O-β-L-rhanmopyranosyl- （1 → 2）-[β-D-xylopyranosyl（1 → 4）]-[-β-D-glucopyranoside, were isolated from the Ophiopogon japonicus （L.f.） Ker-Gaw. Their structures were elucidated by spectroscopic methods.     

Iriterpene glycosides of Astragalus and their genins XLIII. Cycloaraloside B from Astragalus amarus

The structure of a new cycloartane glycoside, cycloaraloside B, isolated from the roots ofAstragalus amarus Pall. (Leguminosae) has been established on the basis of chemical transformations and spectral characteristics: it is 20R,24S-epoxycycloartane-3β,6α,16β,25-tetraol 3-O-[O-α-L-rhamnopyranosyl-(1→2)-(6-O-acetyl-β-D-glucopyranoside)].     

Two new polyhydroxylated triterpenoids from Salvia urmiensis and their cytotoxic activity

Two new polyhydroxylated triterpenoids were isolated from the acetone extract of the aerial parts of Salvia urmiensis Bunge. Their structures were elucidated by 1D and 2D NMR and HR-ESI-MS analyses as olean-12-ene-1β,3β,11α,22α-tetraol (1) and urs-12-ene-1β,3β,11β,22α-tetraol (2). The effect of these compounds on cell viability of MCF-7 cells was investigated by the MTT assay. Compounds 1 and 2 showed weak cytotoxicity with IC₅₀ values of 110.23 ± 0.12 and 88.35 ± 0.09 μM, respectively.