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.     

锥序蜜心果中酚性成分的研究

从锥序蜜心果的乙酸乙酯部分中分离到5个化合物,通过波谱数据或与已知化合物对照,它们分别鉴定为(E)-3-(3-hydroxy-4-methoxyphenyl)acrylic acid carboxymethyl ester(1),3,4-二羟基苯甲酸(2),槲皮素-3-O-β-葡萄糖甙(3),山萘酚-3-O-α-鼠李糖甙(4)和槲皮素-3-O-α-鼠李糖甙(5),以上化合物均为首次从该属植物中分离到.     

广东土牛膝的化学成分

广东土牛膝为菊科泽兰属植物华泽兰（Eupatorium chinense）的干燥根。从其甲醇提取物中共分离得到11个化合物,其中eupatorinA（1）为一新化合物,经波谱学方法鉴定为（threo）-3-O-acetyl-1-（4-hydroxy-3-methoxyphenyl）-2-[4-（3-hydroxy-1-（E）-propenyl）-2,6-dimethoxyphenoxy]propyl-β-D-glucopy-ranoside。已知化合物分别鉴定为（threo）-3-hydroxy-1-（4-hydroxy-3-methoxyphenyl）-2-[4-（3-hydroxy-1-（E）-propenyl）-2,6-dimethoxyphenox-y]-propyl-β-D-glucopyranoside（2）,ardisiacrispinA（3）,ardisiac-rispinB（4）,euparone（5）,3-（2,3-dihydroxy-isopen-tyl）-4-hydroxyacetophenone（6）,12,13-di-hydroxy-euparin（7）,gymnastone（8）,N-（2′-hydroxy-tetracosanosyl）-2-amino-1,3,4-trihydroxy-octa-dec-8-（E）-ene（9）,stigmasterol（10）和stigmasterol-3-O-β-D-glucopyranoside（11）。化合物2-4为首次从菊科植物,5-8为首次从泽兰属植物中分离得到。     

Diarylheptanoids from the rhizomes of Zingiber officinale

Seven new diarylheptanoids, i.e., (3S,5S)-3,5-diacetoxy-1,7-bis(4-hydroxy-3-methoxyphenyl)heptane, (3R,5S)-3-acetoxy-5-hydroxy-1,7-bis(4-hydroxy-3-methoxyphenyl)heptane, (3R,5S)-3,5-dihydroxy-1-(4-hydroxy-3,5-dimethoxyphenyl)-7-(4-hydroxy-3-methoxyphenyl)heptane, (5S)-5-acetoxy-1,7-bis(4-hydroxy-3-methoxyphenyl)heptan-3-one, 5-hydroxy-1-(3,4-dihydroxy-5-methoxyphenyl)-7-(4-hydroxy-3-methoxyphenyl)heptan-3-one, 5-hydroxy-1-(4-hydroxy-3-methoxyphenyl)-7-(3,4-dihydroxy-5-methoxy-phenyl)heptan-3-one and 1,5-epoxy-3-hydroxy-1-(4-hydroxy-3,5-dimethoxyphenyl)-7-(4-hydroxy-3-methoxyphenyl)heptane were isolated from the rhizomes of Chinese ginger (Zingiber officinale Roscoe), along with 25 known compounds, i.e., 8 diarylheptanoids, 14 gingerol analogs, a diterpene and 2 steroids. Their structures were elucidated by spectroscopic and chemical methods.     

New antioxidative phenolic glycosides isolated from Kokuto non-centrifuged cane sugar

Nine compounds, 3-hydroxy-4,5-dimethoxyphenyl-beta-D-glucopyranoside (1), beta-D-fructfuranosyl-alpha-D-(6-vanilloyl)-glucopyranoside (2), beta-D-fructfuranosyl-alpha-D-(6-syringyl)-glucopyranoside (3), 3-hydroxy-1-(4-hydroxy-3-methoxyphenyl)-2-[4-(3-hydroxy-1-(E)-propenyl)-2-methoxyphenoxy]propyl-beta-D-glucopyranoside (4), 3-hydroxy-1-(4-hydroxy-3-methoxyphenyl)-2-[4-(3-hydroxy-1-(E)-propenyl)-2,6-dimethoxyphenoxy] propyl-beta-D-glucopyranoside (5), dehydrodiconiferyl alcohol-9'-beta-D-glucopyranoside (6), 4-[ethane-2-[3-(4-hydroxy-3-methoxyphenyl)-2-propen]oxy]-2,6-dimethoxyphenyl-beta-D-glucopyranoside (7), 4-[ethane-2-[3-(4-hydroxy-3-methoxyphenyl)-2-propen]oxy]-2-methoxyphenyl-beta-D-glucopyranoside (8), and 3-hydroxy-1-(4-hydroxy-3,5-dimethoxyphenyl)-2-[4-(3-hydroxy-1-(E)-propenyl)-2,6-dimethoxyphenoxy]propyl-beta-D-glucopyranoside (9), were isolated from Kokuto non-centrifuged cane sugar. Their structures were elucidated by spectroscopic evidence, mainly based on the NMR technique. Among them, seven new glycosides were identified. The 2-deoxyribose oxidation method was used to measure their antioxidative activity. All of these compounds showed antioxidative activities.     

Lignans of Larix leptolepis

Five lignans have been isolated from wood of Larix leptolepis. They are identified as 1-(4-hydroxy-3-methoxyphenyl)-2-4-[2-formyl-(E)-vinyl]-2-methoxyphenoxy-propane- 1,3-diol, 1-(4-hydroxy-3-methoxyphenyl)-2-2-methoxy-4-[1-(E)-propen-3-ol]-phenoxy- propane-1,3-diol, 1-(4-hydroxy-3-methoxyphenyl)-2-(4-formyl-2-methoxyphenoxy)-propane-1,3-diol, 1,2-bis-(4-hydroxy-3-methoxyphenyl)-propane-1,3-diol and a trilignol, leptolepisol C.     

Studies on Lignin

Two new phenylpropane derivatives, 1-(4-hydroxy-3-methoxyphenyl)-propanediol-(1, 2) and 1-(4-hydroxy-3-methoxyphenyl)-propanediol-(1, 3) were synthesized as lignin model compounds. The former was prepared from 2-acetoxy-1-(4-acetoxy-3-methoxyphenyl)-propanone-(1), and the latter from 3-acetoxy-1-(4-acetoxy-3-methoxyphenyl)-propanone-(1) by lithium aluminum hydride reduction, respectively. The two diols were obtained as colorless syrup, their ultraviolet spectra were determined and crystalline derivatives also prepared.     

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。     

Diarylpropanes from Iryanthera coriacea

The trunk wood of Iryanthera coriacea Ducke (Myristicaceae) contains six compounds which belong to the recently discovered 1,3-diarylpropane type of flavonoids, 1-(2-hydroxy-4-methoxyphenyl)-3-(3,4-methylenedioxyphenyl)-propane, 1-(2,4-dihydroxyphenyl)-3-(3,4-methylenedioxyphenyl)-propane, 1-(4-methoxyphenyl)-3-(2-hydroxy-4,5-methylenedioxyphenyl)-propane, 1-(4-hydroxy-2-methoxy-phenyl)-3-(4-hydroxy-3-methoxyphenyl)-propane, 1-(2,4-dihydroxyphenyl)-3-(2-methoxy-4,5-methylene-dioxyphenyl)-propane, 1-(2,4-dihydroxy-3,5-methylphenyl)-3-(2-hydroxy-4,5-methylenedioxyphenyl)-propane.     

Phenolic constituents from the core of kenaf (Hibiscus cannabinus)

Four lignans, boehmenan H [2-(4-hydroxy-3-methoxyphenyl)-5-[3-(4-hydroxy-3-methoxycinnamoyloxy)propyl]-3-hydroxymethyl-7-methoxybenzodihydrofuran], boehmenan K [2-(4-hydroxy-3-methoxyphenyl)-5-[3-(4-hydroxycinnamoyloxy)-1-propenyl]-3-(4-hydroxy-3-methoxycinnamoyloxymethyl)-7-methoxybenzodihydrofuran], threo-carolignan H [threo-1-(4-hydroxy-3-methoxyphenyl)-2-[4-[3-(4-hydroxy-3-methoxycinnamoyloxy)propyl]-2-methoxyphenoxy]-1,3-propanodiol], and threo-carolignan K [threo-1-(4-hydroxy-3-methoxyphenyl)-3-(4-hydroxy-3-methoxycinnamoyloxy)-2-[4-[3-(4-hydroxycinnamoyloxy)-1-propenyl]-2-methoxyphenoxy]-1-propanol] as well as several other lignans, aldehydes and a tyramine derivative were isolated from the acetone extract of core of kenaf (Hibiscus cannabinus). All the structures were established by spectroscopic methods. The hitherto unreported 13C NMR spectra of some compounds are also presented and discussed. 2D NMR techniques have allowed the revision of certain previously reported 13C NMR assignments of some scarce naturally occurring compounds.     

Neuroprotective phenylpropanoid esters of rhamnose isolated from roots of Scrophularia buergeriana

Four phenylpropanoid esters of rhamnose, buergerisides A1, B1, B2 and C1 were isolated from roots of Scrophularia huergeriana MIQ. (Scrophulariaceae), and were characterized as 2-O-acetyl-3,4-di-O-(E)-p-methoxycinnamoyl-alpha-L-rhamnopyranosid e, 2-O-acetyl-3-O-(E)-p-methoxycinnamoyl-alpha-L-rhamnopyranoside, 2-O-acetvl-3-O-(Z)-p-methoxycinnamoyl-alpha-L-rhamnopyranosi de and 4-O-(E)-p-methoxycinnamoyl-alpha-L-rhamnopyranoside, respectively. In addition, six known phenylpropanoids were authenticated as: (E)-cinnamic acid, (E)-p-methoxycinnamic acid, (E)-p-methoxycinnamic acid methyl ester, (E)-p-coumaric acid, (E)-caffeic acid, (E)-ferulic acid and a phenylalcohol, 2-(3-hydroxy-4-methoxyphenyl)ethanol. These ten phenylpropanoids all attenuated glutamate-induced neurotoxicity when added to primary cultures of rat cortical cells in a dose-dependent manner. These results demonstrate that phenylpropanoids isolated from S. buergeriana may exert significant protective effects against glutamate-induced neurodegeneration in primary cultures of cortical neurons.     

Dilignol glycosides from needles of Picea abies

(2R,3R)-2 3-Dihydro-2-(4′-hydroxy-3′-methoxyphenyl)-3-(hydroxymethyl)-7-methoxy-5-benzofuranpropanol 4′-O-β-d-glucopyranoside [dihydrodehydrodiconiferyl alcohol glucoside], (2R,3R)-2 3-dihydro-7-hydroxy-2-(4′-hydroxy-3′-methoxyphenyl)-3-(hydroxymethyl)-5-benzofuranpropanol 4′-O-β-d-glucopyranoside and 4′-O-α-l-rhamnopyranoside, 1-(4′-hydroxy-3′-methoxyphenyl)-2- [2″-hydroxy-4″-(3-hydroxypropyl)phenoxy]-1, 3-propanediol 1-O-β-d-glucopyranoside and 4′-O-β-d-xylopyranoside, 2,3-bis[(4′-hydroxy-3′-methoxyphenyl)-methyl]-1,4-butanediol 1-O-β-d-glucopyranoside [(?)-seco-isolariciresinol glucoside] and (1R,2S,3S)-1,2,3,4-tetrahydro-7-hydroxy-1-(4′-hydroxy-3′-methoxyphenyl)-6-methoxy-2 3-naphthalenedimethanol α²-O-β-d-xylopyranoside [(?)-isolariciresinol xyloside] have been isolated from needles of Picea abies and identified.     

Constitutions of diarylpropanoids from Virola multinervia

The wood of Virola multinervia Ducke (Myristicaceae) contains sitosterol, stigmasterol and two novel diarylpropanoids virolane [1-(2-hydroxy-4-methoxyphenyl)-3-(3,4-methylenedioxyphenyl)-propane] and virolanol [2-hydroxy-1-(2-hydroxy-4-methoxyphenyl)-3-(3,4-methylenedioxyphenyl)-propane].     

Inhibition of lipid peroxidation and protein oxidation in rat liver mitochondria by curcumin and its analogues

Curcumin (1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione, 1) is a yellow ingredient isolated from turmeric (curcumin longa). It has been shown to exhibit a variety of biological activities including antioxidative activity. In order to find more active antioxidants with 1 as the lead compound we synthesized curcumin analogues, i.e., 1-(3,4-dihydroxyphenyl)-7-(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione (2), 1-(4-hydroxy-3-methoxyphenyl)-7-(4-hydroxyphenyl)-1,6-heptadiene-3,5-dione (3), 1,7-bis-(4-hydroxyphenyl)-1,6-heptadiene-3,5-dione (4), 1-(3,4-dimethoxyphenyl)-7-(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione (5), 1,7-bis(3,4-dimethoxyphenyl)-1,6-heptadiene-3,5-dione (6), and 1,7-diphenyl-1,6-heptadiene-3,5-dione (7), and evaluated their antioxidative activity. The in vitro oxidative damage to both lipids and proteins in rat liver mitochondria was used as a model to study the free radical-induced oxidative damage of biological lipids as well as proteins and the protective effects of these curcumin analogues. It was found that these compounds, except 6 and 7, could effectively inhibit the free radical induced lipid peroxidation and protein oxidative damage of rat liver mitochondria by H-atom abstraction from the phenolic groups. Compound 2 which bear ortho-diphenoxyl functionality exhibited remarkably higher antioxidative activity for lipids and proteins than curcumin and other analogues, and the 4-hydroxy-3-methoxyphenyl group also play an important role in the antioxidative activity.     

柯拉斯那沉香中2-(2-苯乙基)色酮类化学成分研究

为研究柯拉斯那(Aquilaria crassna Pierre ex Lecomte)沉香的化学成分。实验采用多种柱色谱方法从该沉香中分离得到9个2-(2-苯乙基)色酮类化合物,通过现代波谱学技术分别鉴定为6-甲氧基-2-[2-(3′-羟基-4′-甲氧基苯基)乙基]色酮(1)、5-羟基-6-甲氧基-2-[2-(3′-羟基-4′-甲氧基苯基)乙基]色酮(2)、tetrahydrochromone F(3)、6-甲氧基-2-[2-(3′-甲氧基-4′-羟基苯基)乙基]色酮(4)、6-甲氧基-7-羟基-2-[2-(4′-甲氧基苯基)乙基]色酮(5)、6,7-二甲氧基-2-[2-(3′-羟基-4′-甲氧基苯基)乙基]色酮(6)、6,7-二甲氧基-2-[2-(4′-甲氧基苯基)乙基]色酮(7)、6-羟基-2-[2-(4′-羟基苯基)乙基]色酮(8)、5-羟基-2-[2-(2′-羟基苯基)乙基]色酮(9)。化合物2、3和5～9均为首次从柯拉斯那所得沉香中分离得到。采用MTT法对单体化合物的细胞毒活性进行测试,测试结果表明,化合物1,2和4具有微弱的细胞毒活性。     

Characterization of novel glycolipids from the giant cockroach (Blaberus colosseus)

A novel class of glycolipids, assigned the trivial name blaberosides, was isolated from whole head tissues of the giant cockroach (Blaberus colosseus). The class consists of two closely related families, blaberoside I and blaberoside II, each containing species differing by 26 atomic mass units. The structure of these gentiobiose-based glycoglycerolipids was elucidated by chromatographic behavior, nuclear magnetic resonance spectroscopy, mass spectrometry, and analysis of chemical degradation products and derivatives. Species in the blaberoside I family have been identified as 2-O-[6'-O-(6"-O-3-hydroxy-11-eicosenoyl-beta-D-glucopyranosyl)-bet a-D- glucopyranosyl]-3-(hexadecyloxy)-1-(3-hydroxy-11-eicosenoyl)-1,2-p ropanediol (blaberoside Ia) and 2-O-[6'-O-(6"-O-3-hydroxy-11-eicosenoyl-beta-D-glucopyranosyl)-bet a- D-glucopyranosyl]-3-(6-octadeceloxy)-1-(3-hydroxy-11-eicosenoyl )-1,2- propanediol (blaberoside Ib). Two smaller homologs of the blaberoside II family were discerned to be 2-O-[6'-O-(6"-O-3-hydroxy-11- eicosenoyl-beta-D-glucopyranosyl)-beta-D-glucopyranosyl]-3-(hex ade cyloxy)- 1,2-propanediol (blaberoside IIa), and 2-O-[6'-O-(6"-O-3-hydroxy-11-eicosenoyl-beta-D- glucopyranosyl)-beta-D-glucopyranosyl]-3-(4-octadeceloxy)-1,2-prop anediol (blaberoside IIb). These compounds are unique because they are animal origin glyceroglycolipids with a highly flexible gentiobiose backbone, and a beta-linkage of the carbohydrate to the glycerol ether at the 2 position rather than the usual 1 position.     

Studies on Lignin

2-Ethylthio-1-(4-hydroxy-3-methoxyphenyl)-propanone-(1) (I) which has been previously isolated from mercaptolysis oil of pine ethanol lignin was also obtained from mercaptolysis oil of spruce wood. 1-Ethylthio-1-(4-hydroxy-3-methoxyphenyl)-propanone-(2) (II), synthesis of which has been reported before, was found to be converted into (I) on mercaptolysis.     

Antioxidative phenylpropanoids from berries of Pimenta dioica

A phenylpropanoid, threo-3-chloro-1-(4-hydroxy-3-methoxyphenyl)propane-1,2-diol, was isolated from the berries of Pimenta dioica together with five known compounds, eugenol, 4-hydroxy-3-methoxycinnamaldehyde, 3,4-dimethoxycinnamaldehyde, vanillin and 3-(4-hydroxy-3-methoxyphenyl)propane-1,2-diol. In addition, the stereochemistry of 3-(4-hydroxy-3-methoxyphenyl)propane-1,2-diol was determined. The phenylpropanoids inhibited autoxidation of linoleic acid in a water-alcohol system.     

Determination of diarylheptanoids from Alpinia officinarum (Lesser Galangal) by HPLC with photodiode array and electrochemical detection

Normal-phase column chromatography followed by semi-preparative reversed-phase HPLC has been used to isolate, from the rhizomes of Alpinia officinarum, five diarylheptanoids identified as 5-hydroxy-7-(4"-hydroxy-3"-methoxyphenyl)-1-phenyl-3-heptanone, 5-methoxy-7-(4"-hydroxy-3"-methoxyphenyl)-1-phenyl-3-heptanone, 7-(4"-hydroxyphenyl)-1-phenylhept-4-en-3-one, 7-(4"-hydroxy-3"-methoxyphenyl)-1-phenyl-hept-4-en-3-one, 1,7-diphenylhept-4-en-3-one. The levels of these five diarylheptanoids in root material were determined quantitatively by HPLC with UV detection and the assay methods so developed were simple, rapid and accurate. Four of the diarylheptanoids could also be detected by HPLC with electrochemical detection (ECD) in the oxidative mode, and ECD was found to have a higher sensitivity than photodiode array detection.     

Phytotoxic cis-cinnamoyl glucosides from Spiraea thunbergii

Spiraea thunbergii Sieb. was found to contain 1-O-cis-cinnamoyl-beta-D-glucopyranose and 6-O-(4'-hydroxy-2'-methylene-butyroyl)-1-O-cis-cinnamoyl-beta-D-glucopyranose as major plant growth inhibitory constituents along with related compounds of lower phytotoxicity including 6-O-(trans-cinnamoyl)-1-O-(4"-hydroxy-3"-methyl-furan-2"-one)-beta-D-glucopyranose, 6-O-(4'-hydroxy-2'-methylene-butyroyl)-1-O-trans-cinnamoyl-beta-D-glucopyranose, and 1-O-trans-cinnamoyl-beta-D-glucopyranose. The former three compounds were cinnamoyl glucosides.