湖北旋覆花化学成分的研究(英文)

从湖北旋覆花(Inula hupehensis)地上部分分离得到19个化合物,经波谱数据分析分别鉴定为9-羟基-百里香酚(1),8,10-去氢-β-羟基-百里香酚(2),2-羟基-4-甲基苯乙酮(3),8,9-双羟基-9-百里香酚(4),10-羟基-8,9-双氧亚异丙基百里香酚(5),8,10-二羟基-9-异丁酰百里香酚(6),8-羟基-9-异丁酰-10-(2-甲基丁酰)百里香酚(7),8,9,10-三羟基百里香酚(8),8-羟基-9,10-二异丁酰百里香酚(9),neoechinulin A(10),3-醛基吲哚(11),3-羟乙酰基吲哚(12),丁香酸(13),4,6-二羟基-2-甲氧基苯乙酮(14),7-甲氧基-8-羟基香豆素(15),6-甲氧基山奈酚(16),(+)-正丁香酯素(17),β-棕榈精(18)和豆甾醇(19)。除了化合物8和9外,其他化合物均为首次从该植物中分离得到。     

New Withanolides from Nicandra physaloides (Solanaceae)

Two new withanolides, named nicandrenone methyl ether (1), 26S nicandrenone methyl ether (2), together with ten known compounds were isolated from the whole plants of Nicandra physaloides (Solanaceae). Their chemical structures were deduced on the basis of spectroscopic analysis. Ten known compounds were identified as nicandrenone (3), Nic-7 (4), nicaphysalin E (5), pinosylvin monomethyl ether (6), 2S-pinocembrin (7), (1S, 2R)-1, 2-bis (4-hydroxy-3-methoxyphenyl)-1, 3-propanediol (8), vanillin (9), indole-3-carboxylic acid (10), vanillic acid (11) and drummondol (12).     

Neoflavonoids and the cinnamylphenol kuhlmannistyrene from Machaerium kuhlmannii and M. Nictitans

The trunkwood of Machaerium kuhlmannii contains methyl palmitate, 3-O-acetyloleanolic acid and sitosterol; the benzene derivatives 2,3-dimethoxyphenol, 2,6-dimethoxyphenol, 2-hydroxy-3-methoxyphenol, 2,3-dimethoxybenzaldehyde and methyl 3-(2-hydroxy-4-methoxyphenyl)-propionate; the isoflavonoids formononetin and (6aS,11aS)-medicarpin; the neoflavonoids (R)-3,4-dimethoxydalbergione, (R)-3,4-dimethoxydalbergiquinol, kuhlmanniquinol [(R)-3-(4-hydroxyphenyl)-3-(5-hydroxy-2,3,4-trimethoxyphenyl)-propene], dalbergin, kuhlmannin (6-hydroxy-7,8-dimethoxy-4-phenylcoumarin) and kuhlmannene (6-hydroxy-7,8-dimethoxy-4-phenylchrom-3-ene), as well as the cinnamylphenol kuhlmannistyrene [Z-1-(5-hydroxy-2,3,4-trimethoxybenzyl)-2-(2-hydroxyphenyl)-ethylene]. Five of these compounds, in addition to (R)-4′-hydroxy-3,4-dimethoxydalbergione, were also isolated from a trunkwood extract of M. nictitans. Structural assignments were confirmed by chemical interconversion and by the synthesis of (±)-kuhlmanniquinol.     

Three new phenolic acid derivatives from Oenothera biennis

Three new phenolic acid derivatives, 1-methyl glyceric acid-2-vanillic acid ether (1), methyl 2-hydroxy-6-(3-methoxy-3-oxoprop-1-en-2-yloxy) benzoate (2), methyl 2-hydroxy-6-(1-Carboxyvinyloxy) benzoate (3) and five known compounds namely 4-hydroxymellein (4), mellein methyl ether (5), 2-methyl-5,7-dihydroxychromone (6), latifolicinin C (7) and oresbiusin A (8) were isolated from Oenothera biennis L. The structures of these secondary metabolites were elucidated using different spectroscopic techniques, including ¹H, ¹³C NMR, HR-ESI-MS, ECD and comparison with published data.     

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。     

Novel extracellular enzymes (ligninases) of Phanerochaete chrysosporium

Abstract 3 New spectrophotometric enzyme assays were developed for the study of microbial lignin-degrading enzymes. The conversion of 2-methoxy-3-phenylbenzoic acid to 2-hydroxy-3-phenylbenzoic acid led to the discovery of an extracellular, aromatic methyl ether demethylase produced by the white-rot fungus Phanerochaete chrysosporium . The conversion of methyl 2-hydroxy-3-phenylbenzoate to 2-hydroxy-3-phenylbenzoic acid allowed the identification of an extracellular, aromatic methyl ester esterase produced by this fungus. The Phanerochaete sp. also excreted an enzyme complex that oxidized 4-(4-hydroxy-3-methoxyphenyl)-3-buten-2-one, probably to aliphatic products. All 3 novel enzyme activities were produced together with, and probably comprise a part of, the Phanerochaete ligninolytic enzyme complex. Unlike previously known ligninases, these enzymes did not oxidize 3,4-dimethoxybenzyl alcohol. All 3 were H₂O₂-dependent and were activated by Mn²⁺ ions.     

银合欢豆荚中的酚类化学成分

为探讨银合欢(Leucaena leucocephala)的化学成分,从银合欢豆荚乙醇提取物中分离得到7个酚类化合物,经过波谱分析,鉴定为原儿茶酸乙酯(1)、丁香酸(2)、3-羟基-1-(3-甲氧基-4-羟基苯基)丙烷-1-酮(3)、咖啡酸甲酯(4)、(Z)-对香豆醛(5)、3-甲氧基-4-羟苯丙烷-7,8,9-三醇(6)、愈创木基甘油-8-O-4′-芥子醇醚(7)。所有化合物均为首次从该植物中分离得到。化合物1对大肠杆菌和鼠伤沙门氏菌有一定的抑制活性。     

假酸浆中新的醉茄内酯类化合物

从假酸浆（Nicandra physaloides）全草中分离得到12个化合物,其中两个为新的醉茄内酯类化合物,经波谱学方法将其结构鉴定为nicandrenone methyl ether （1） 和26S-nicandrenone methyl ether （2）;已知化合物为三个醉茄内酯,nicandrenone （3）,Nic-7 （4）,nicaphysalin E （5）,以及pinosylvin monomethyl ether （6）,2S-pinocembrin （7）,（1S, 2R）-1, 2-bis （4-hydroxy-3-methoxyphenyl）-1, 3-propanediol （8）,vanillin （9）,indole-3-carboxylic acid （10）,vanillic acid （11） 和drummondol （12）。     

宁夏枸杞根和茎的化学成分及抗炎活性研究

研究宁夏枸杞(Lycium barbarum L.)根部和茎部的化学成分。采用硅胶柱、ODS开放柱、Sephadex LH-20葡聚糖凝胶柱及半制备反相高效液相等色谱手段,对宁夏枸杞根和茎部乙醇提取物的石油醚部位及乙酸乙酯部位化学成分进行分离纯化,根据其理化性质以及波谱数据鉴定得到12个化合物,分别为N-[2-(3,4-dihydroxyphenyl)-2-hydroxyethyl]-3-(4-methoxyphenyl)prop-2-enamide(1)、3-(4-hydroxy-3-methoxy phenyl)-N-2-(4-hydroxyphenyl)-2-methoxyethyl]acrylamide(2)、N-trans-coumaroyloctopamine(3)、(E)-2-(4,5-dihydroxy-2-{3-[(4-hydroxyphenethyl)amino]-3-oxopropyl}phenyl)-3-(4-hydroxy-3,5-dimethoxyphenyl)-N-(4-acetamidobutyl)acrylamide(4)、1,2-dihydro-6,8-dimethoxy-7-hydroxy-1-(3,4-dihydroxy-phenyl)-N1,N2-bis[2-(4-hydroxyphenyl)ethyl]-2,3-naphthalene dicarboxamide(5)、(+)-syringaresinol(6)、zhebeiresinol(7)、(±)-eriodictyol(8)、isovanilin(9)、5,5′-dimethoxybiphenyl-2,2′-diol(10)、p-hydroxyphenethyltrans-ferulate(11)、E-ferulic acid hexacosyl ester(12),所有化合物均为首次从该植物中分离得到。此外,采用MTT法和抑制一氧化氮(NO)生成实验,从细胞毒活性和抗炎活性两方面评估了化合物的生物活性。结果表明,化合物2具有显著的抗炎活性,其IC50值(17.00±1.11μmol/L)小于阳性对照药槲皮素的IC50值(17.21±0.50μmol/L)。     

Commercially processed dry ginger (Zingiber officinale): composition and effects on LPS-stimulated PGE2 production

Using techniques previously employed to identify ginger constituents in fresh organically grown Hawaiian white and yellow ginger varieties, partially purified fractions derived from the silica gel column chromatography and HPLC of a methylene chloride extract of commercially processed dry ginger, Zingiber officinale Roscoe, Zingiberaceae, which demonstrated remarkable anti-inflammatory activity, were investigated by gas chromatography-mass spectrometry. In all, 115 compounds were identified, 88 with retention times (R(t)) >21 min and 27 with <21 min. Of those 88 compounds, 45 were previously reported by us from fresh ginger, 12 are cited elsewhere in the literature and the rest (31) are new: methyl [8]-paradol, methyl [6]-isogingerol, methyl [4]-shogaol, [6]-isoshogaol, two 6-hydroxy-[n]-shogaols (n=8 and 10), 6-dehydro-[6]-gingerol, three 5-methoxy-[n]-gingerols (n=4, 8 and 10), 3-acetoxy-[4]-gingerdiol, 5-acetoxy-[6]-gingerdiol (stereoisomer), diacetoxy-[8]-gingerdiol, methyl diacetoxy-[8]-gingerdiol, 6-(4'-hydroxy-3'-methoxyphenyl)-2-nonyl-2-hydroxytetrahydropyran, 3-acetoxydihydro-[6]-paradol methyl ether, 1-(4'-hydroxy-3'-methoxyphenyl)-2-nonadecen-1-one and its methyl ether derivative, 1,7-bis-(4'-hydroxy-3'-methoxyphenyl)-5-methoxyheptan-3-one, 1,7-bis-(4'-hydroxy-3'-methoxyphenyl)-3-hydroxy-5-acetoxyheptane, acetoxy-3-dihydrodemethoxy-[6]-shogaol, 5-acetoxy-3-deoxy-[6]-gingerol, 1-hydroxy-[6]-paradol, (2E)-geranial acetals of [4]- and [6]-gingerdiols, (2Z)-neral acetal of [6]-gingerdiol, acetaldehyde acetal of [6]-gingerdiol, 1-(4-hydroxy-3-methoxyphenyl)-2,4-dehydro-6-decanone and the cyclic methyl orthoesters of [6]- and [10]-gingerdiols. Of the 27 R(t)<21 min compounds, we had found 5 from fresh ginger, 20 others were found elsewhere in the literature, and two are new: 5-(4'-hydroxy-3'-methoxyphenyl)-pent-2-en-1-al and 5-(4'-hydroxy-3'-methoxyphenyl)-3-hydroxy-1-pentanal. Most of the short R(t) compounds are probably formed by thermal degradation during GC (which mimics cooking) and/or commercial drying. The concentrations of gingerols, the major constituents of fresh ginger, were reduced slightly in dry ginger, while the concentrations of shogaols, the major gingerol dehydration products, increased.     

Metabolism of Lignin Model Compounds of the Arylglycerol-beta-Aryl Ether Type by Pseudomonas acidovorans D(3)

A natural bacterial isolate that we have classified as Pseudomonas acidovorans grows on the lignin model compounds 1-(3,4-dimethoxyphenyl)-2-(2-methoxyphenoxy)propane-1,3-diol (compound 1) and 1-(4-hydroxy-3-methoxyphenyl)-2-(2-methoxyphenoxy)propane-1,3-diol (compound 1'), as well as on the corresponding 1-oxo compounds (2 and 2') as sole sources of carbon and energy. Metabolic intermediates present in cultures growing on compound 1 included compound 2, 2-methoxyphenol (guaiacol [compound 3]), beta-hydroxypro-pioveratrone (compound 4), acetoveratrone (compound 5), and veratric acid (compound 6). Also identified were compounds 1', 2', beta-hydroxypropiovanillone (compound 4'), and acetovanillone (compound 5'), indicating that 4-O demethylation also occurs. The phenolic intermediates were the same as those found in cultures growing on compound 1'. Compounds 2 and 2' were in part also reduced to compounds 1 and 1', respectively. Compound 3 was shown to be derived from the 2-methoxyphenoxy moiety. A suggested degradation scheme is as follows: compound 1-->2-->(3 + 4)-->5-->6 (and similarly for 1'). In this scheme, the key reaction is cleavage of the ether linkage between C-2 (C(beta)) of the phenylpropane moiety and the 2-methoxyphenoxy moiety in compounds 2 and 2' (i.e., beta-aryl ether cleavage). On the basis of compounds identified, viz., 3 and 4 (4'), cleavage appears formally to be reductive. Because this is unlikely, the initial cleavage products probably were not detected. The implications of these results for the enzyme(s) responsible are discussed.     

Successive Isolation of Proteinase Hyperproductive Mutants of Aspergillus sojae

Hydrochloric acid treatment of methyl 3-(4-isobutylphenyl)-3-methylglycidate and methyl 2-hydroxy-3-(4-isobutylphenyl)-3-butenoate, a rearrangement product of the former, in acetic acid gave 3-(4-isobutylphenyl)-3-methylpyruvic acid and 2-(4-isobutylphenyl)-pro-panal. The same treatment of 2-hydroxy-3-(4-isobutylphenyl)-3-butenoic acid gave 2-(4-isobutylphenyl)-propanal. Both 3-(4-isobutylphenyl)-3-methylpyruvic acid and 2-(4-iso-butylphenyl)-propanal were oxidized to 2-(4-isobutylphenyl)-propionic acid.     

Low-molecular-weight components of olive oil mill waste-waters

A new lignan 1-hydroxy-2-(4-hydroxy-3-methoxyphenyl)-6-(3-acetyl-4-hydroxy-5-methoxyphenyl)-3,7-dioxabicyclo[3.3.0]octane, the secoiridoid 2H-pyran-4-acetic acid,3-hydroxymethyl-2,3-dihydro-5-(methoxycarbonyl)-2-methyl-, methyl ester, the phenylglycoside 4-[beta-D-xylopyranosyl-(1-->6)]-beta-D-glucopyranosyl-1,4-dihydroxy-2-methoxybenzene and the lactone 3-[1-(hydroxymethyl)-1-propenyl] delta-glutarolactone were isolated and identified on the basis of spectroscopic data including two-dimensional NMR, as components of olive oil mill waste-waters. The known aromatic compounds catechol, 4-hydroxybenzoic acid, protocatechuic acid, vanillic acid, 4-hydroxy-3,5-dimethoxybenzoic acid, 4-hydroxyphenylacetic acid, 3,4-dihydroxyphenylacetic acid, tyrosol, hydroxytyrosol, 2-(4-hydroxy-3-methoxy)phenylethanol, 2-(3,4-dihydroxy)phenyl-1,2-ethandiol, p-coumaric acid, caffeic acid, ferulic acid, sinapic acid, 1-O-[2-(3,4-dihydroxy)phenylethyl]-(3,4-dihydroxy)phenyl-1,2-ethandiol, 1-O-[2-(4-hydroxy)phenylethyl]-(3,4-dihydroxy)phenyl-1,2-ethandiol, D(+)-erythro-1-(4-hydroxy-3-methoxy)-phenyl-1,2,3-propantriol, p-hydroxyphenethyl-beta-D-glucopyranoside,2(3,4-dihydroxyphenyl)ethanol 3beta-D-glucopyranoside, and 2(3,4-dihydroxyphenyl)ethanol 4beta-D-glucopyranoside were also confirmed as constituents of the waste-waters.     

Norlignans from Pouzolzia occidentalis

Two structurally interesting new norlignans named 2-hydroxy-4-[4-hydroxyphenyl-(4-hydroxy-3-methoxybenzyl)]-3-(3,5-dihydroxyphenyl)tetrahydrofuran (1) (pouzolignan A), and 1,4-dihydroxy-3-[4-hydroxyphenyl-(4-hydroxy-3-methoxybenzyl)]-2-(3,5-dihydroxyphenyl)butane (2) (pouzolignan B), were isolated from the EtOAc fraction of the methanol extract of Pouzolzia occidentalis. Compound 3, the methyl ether of 1, most likely an artifact, was also isolated. The overall structures and relative stereochemistry were elucidated largely by analysis of 1D and 2D NMR spectral data.     

Chemical Constituents of Phacellaria compressa Benth.

Two new compounds, 1-（3-methoxy-4-hydroxyphenyl）-3-（3,5-dimethoxy-4-hydroxyphenyl）-propane （1） and 5, 7, 3＇-trlmethyoxyflavan-4＇-O-β-D-glucopyranoslde （2） were Isolated from the ethanol extract of the dried aerial parts of Phacellarla compressa Benth., together with 2,3-bis[（4-hydroxy-3,5-dimethoxyphenyl）-methyl]-1,4- butanedlol （3）, ethyl 3,4,5-trlhydroxybenzoate （4）, methyl 3, 4, 5-trlhydroxybenzoete （5）, β-sltoeterol （6）, 5, 7, 3＇, 4＇- tetrahydroxyfiavan （7）, lupeol （8）, zhebelreslnol （9）, quercetln-3-O-α-L-rhamnopyranoslde （10）, （＋）-cetechin （11）, betulln （12）, β-daucosterol （13）, （＋）-sydngareslnol （14）, scopoletln （15）, and proxlmadlol （16）. The structures of these compounds were determined by spectral evidence or by comparing them with authentic samples. Compound 9 showed α-amylase Inhibitory activity of 57.55% at a concentration of 50 μg/mL.     

唐古特瑞香的化学成分研究

从唐古特瑞香(Daphne tangutica Maxim)95%乙醇提取物石油醚部分分离得到14个化合物,通过波谱学方法鉴定为β-谷甾醇(1)、β-胡萝卜苷(2)、2,4-二羟基-3,6-二甲基苯甲酸甲酯(3)、蛇床子素(4)、植物醇(5)、软脂酸(6)、stigmast-5-ene-3β,7α-diol(7)、(-)-lariciresinol(8)、daphnetin(9)、daphnoretin(10)、(-)-丁香树脂醇(11)、( )-medioresinol(12)、daphnelicin(13)和咖啡酸二十二酯(14)。     

隔山消化学成分的研究

从隔山消的石油醚部分分离得到6个芳香类化合物,分别鉴定为2,4-二羟基苯乙酮（1-（2,4-dihy—droxph—enyl）ethanone,1）、奎乙酰苯（acetylquinol,2）、对羟基苯乙酮（1-（4-hydroxyphenyl）ethanone,3）、4-羟基-3-甲氧基苯乙酮（1-（4-hydroxy-3-methoxyphenyl）ethanone,4）、2,4-二羟基-5-甲氧基苯乙酮（1-（2,4-dihydroxy-5-methoxyphenyl）ethanone,5）、3-羟基4-甲氧基苯甲酸（3-hydroxy-4-methoxy—benzoicacid,6）。除化合物2外,其余5个化合物均首次从该植物中分离得到。     

Studies toward a conjugate vaccine for anthrax. Synthesis and characterization of anthrose [4,6-dideoxy-4-(3-hydroxy-3-methylbutanamido)-2-O-methyl-D-glucopyranose] and its methyl glycosides

The key step in the first chemical synthesis of anthrose (16) and its methyl alpha- (6) and beta-glycoside (22) was inversion of configuration at C-2 in triflates 10, 2, and 18, respectively, obtained from the common intermediate, methyl 4-azido-3-O-benzyl-4,6-dideoxy-alpha-D-mannopyranoside (1). To prepare methyl alpha-anthroside (6), methylation at O-2 of the gluco product 3, obtained from 2, was followed by hydrogenation/hydrogenolysis of the formed 2-methyl ether 4, to simultaneously remove the protecting benzyl group and reduce the azido function. Subsequent N-acylation of the formed amine 5 with 3-hydroxy-3-methylbutyric acid gave the target methyl alpha-glycoside 6. Synthesis of methyl beta-anthroside (22) comprised the same sequence of reactions, starting from the known methyl 4-azido-3-O-benzyl-4,6-dideoxy-beta-D-mannopyranoside (17), which was prepared from 1. In the synthesis of anthrose (16), 1-thio-beta-glucoside 11, obtained from 1 through 10, was methylated at O-2, and the azido function in the resulting benzylated 1-thioglycoside 12 was selectively reduced to give amine 13. After N-acylation with 3-hydroxy-3-methylbutyric acid, 1-thioglycoside 14 was hydrolyzed to give the corresponding reducing sugar, aldol 15, which was debenzylated to afford anthrose.     

New phenolics from the wood of Casearia grewiifolia

Two new phenolic compounds, threo-2,3-bis(4-hydroxy-3-methoxyphenyl)-3-butoxypropan-1-ol (1) and erythro-2,3-bis(4-hydroxy-3-methoxyphenyl)-3-butoxypropan-1-ol (2) were isolated from the wood of Casearia grewiifolia together with eight known compounds, N-trans-feruloyltyramine, ω-hydroxypropioguaiacone, C-veratroylglycol, syringaldehyde, vanillic acid, (?)-syringaresinol, β-sitosterol and β-sitosterone. The structures were elucidated by spectroscopic analysis, as well as comparison with literature data. This is the first study to identify the phenolic, amide, lignan and steroid constituents from C. grewiifolia and the new phenolics reported here are the first examples of 2,3-bis(4-hydroxy-3-methoxyphenyl)-1,3-propanoids found in the Caseria genus.     

Inhibition by prostacyclin and carbacyclins of endothelin-induced DNA synthesis in cultured vascular smooth muscle cells

Effects of prostacyclin and carbacyclins on endothelin-induced DNA synthesis were investigated in vascular smooth muscle cells. DNA synthesis was estimated by [3H]thymidine incorporation. Five carbacyclins used in this report were 5-[(1S, 5S, 6R, 7R)-7-hydroxy-6-[(E)-(S)-3-hydroxy-1-octenyl]bicyclo [3.3.0]oct-2-en-3-yl) pentanoic acid (TEI-7165), methyl 5-[(1S, 5S, 6R, 7R)-7-hydroxy-6-[(E)-(S)-3-hydroxy-1-octenyl]bicyclo[3.3.0]oct-2-en-3- yl]pentanoate (TEI-9090), 5-[(1S, 5S, 6R, 7R)-7-hydroxy-6-[(E)-(3S, 5S)-3-hydroxy-5-methyl-1-nonenyl]bicyclo[3.3.0]oct-2-en-3-yl)penta noic acid (TEI-9063), methyl 5-[(1S, 5S, 6R, 7R)-7-hydroxy-6-[(E)-(3S, 5S)-3-hydroxy-5-methyl-1- nonenyl]bicyclo[3.3.0]oct-2-en-3-yl)pentanoate (TEI-1324), 5-[(1S, 5S, 6R, 7R)-7-hydroxy-6-[(E)-(S)-4-hydroxy-4-methyl-1- octenyl]bicyclo[3.3.0]oct-2-en-3-yl] pentanoic acid (TEI-3356). Prostacyclin and the carbacyclins inhibited the endothelin-induced DNA synthesis within the nanomolar range. These results suggest that prostacyclin and carbacyclins are possibly effective in inhibiting the proliferation of vascular smooth muscle cells under some situations in vivo.