斑叶紫金牛化学成分的研究（Ⅰ）

采用95%乙醇提取,反复硅胶柱层析分离和光谱、波谱方法鉴定结构,从斑叶紫金牛(Ardisia punctataLindl.)中初步分离鉴定出7个化合物,2-甲基-5-[14(顺)-十九烯基]-1,3-间苯二酚(1),2-甲基-5-壬烷基-1,3-间苯二酚(2),3-0-[6'-O-palmitoyl-β-D-glucosyl-]-spinasta-7,22(23)-diene(3a),3-O-[6'-O-pahnitoyl]-β-D-sin-cosyl-pyranosyl stignmsterol(3b),岩白菜素(4),11-O-(4'-O-methylgalloyl)-bergenin(5),正二十四烷酸(6).所有化合物均为首次从该植物中获得,其中化合物2和6为首次从该属植物中分得.     

真菌Talaromyces stipitatus WH4-2中的抗菌活性成分

【目的】对真菌菌株WH4-2进行鉴定并分离鉴定具有抗菌活性的天然产物。【方法】综合菌落形态和ITS全序列分析,鉴定菌株种属。以抗菌活性分析为导向对其中的活性组分进行分离纯化,波谱分析鉴定结构。采用微量稀释法对化合物进行活性复筛,得最小抑菌浓度MIC值。【结果】真菌菌株WH4-2鉴定为Talaromyces stipitatus。从其土豆发酵液中分离鉴定化合物1 (5S-arugosin K)、2 (5R-arugosin K)、3 (5S-arugosin M)、4 (5R-arugosin M)和5 (Chrysophanol),其中1–4为含异戊烯基的dibenzo[b,e]oxepinone类化合物,5为蒽醌类化合物。1–4对Staphylococcus aureus ATCC43300、ATCC33591,Enterococcus faecium ATCC35667和Bacillussubtilis ATCC6633具有抗菌活性。【结论】含异戊烯基的Dibenzo[b,e]oxepinone类化合物是真菌T. stipitatus中抗菌活性成分。     

木姜子叶精油的化学成分研究

采用气相色谱-质谱联用仪对产于秦岭太白山的木姜子叶的挥发油成分进行分析鉴定,从分离出的79个峰中鉴定了32种成分,其含量占挥发油总量的90.59％,主要成分为1,3,3-三甲基-乙-氧杂双环[2,2,2]辛烷(59.96％),1,8-桉油醇(8.96％),香茅醛(6.86％),2-甲基-5-(1-甲基乙烯基)环己酮(4.34％)和澄花醇乙酯(3.19％)。     

假烟叶树叶挥发油化学成分分析

采用水蒸汽蒸馏法、两相溶剂萃取法提取,运用毛细管气相色谱-质谱联用法结合计算机检索对茄科植物假烟叶树(Solanum verbascifoliumL.)叶挥发油的化学成分进行分析和鉴定。其新鲜叶片提取10 h的挥发油得率为0.0611%。经毛细管色谱分离出18个峰,共鉴定出17种化合物,占挥发油总量的99.73%;用气相色谱面积归一化法计算各组分的相对含量,其主要化学成分为:大牻牛儿烯D(37.07%),咕巴烯(26.29%),1β-(1-甲基乙基)-4,7-二甲基-1α,2,4a()β,5,8,8a()α-六氢萘(13.63%),石竹烯(8.03%),1-β乙烯基-1-α甲基-2,β4-β双(1-甲基乙烯基)-环己烷(5.81%),-γ榄香烯(2.16%),α-筚澄茄油烯(2.06%),异喇叭烯(0.98%)。以上8种化合物占总挥发油含量的90.22%。     

民族药木耳菜挥发油成分和脂溶性成分GC-MS分析

采用水蒸气蒸馏法和索氏提取法提取木耳菜挥发油和脂溶性成分,利用GC-MS技术鉴定挥发油和脂溶性成分。鉴定出47个挥发油成分和20个脂溶性成分。其挥发油成分主要有依兰烯(7.30%)、δ-杜松烯(6.85%)、氧化石竹烯(5.90%)、1,5,9-三甲基-12-(1-甲基乙基)-4,8,13-环戊二烯并环辛四烯-1,3-二醇(5.83%)等。脂溶性成分主要有8,11-十八碳二烯酸甲酯(16.09%)、棕榈酸甲酯(12.15%)、花生酸甲酯(7.06%)、亚麻酸甲酯(7.00%)等。     

下田菊挥发油化学成分的研究

利用水蒸汽蒸馏法、两相溶剂萃取法提取下田菊(Adenostemma lavenia(L.)O.Ktze.)地上部分的挥发油,提取10h的挥发油得率为0.990%。采用毛细管气相色谱-质谱联用(GC-MS)技术结合计算机检索对该挥发油的化学成分进行了分析和鉴定,采用色谱峰面积归一化法计算了各成分的相对含量。从挥发油中共分离出36个峰,鉴定了其中的35种成分,占总量的99.56%,其中α-荜澄茄油烯(32.62%)、石竹烯(24.97%)和γ-榄香烯(5.53%)为主要成分,此外α-石竹烯(3.97%)、α-恰米烯(3.57%)、双环[4,3,0]-7-亚甲基-2,4,4-三甲基-2-乙烯基-壬烷(3.41%)、γ-萜品烯(3.07%)、d-柠檬烯(2.57%)、α-蒎烯(2.49%)及2-蒈烯(2.28%)的含量也较高。     

中药新疆羌活根中挥发油的化学成分

采用气相色谱-质潜法,从中药新疆羌活(灰绿叶当归加Angelica glauca Edgew.)根挥发油中,分离出47个化合物,共鉴定了32个化合物,其中首次从该植物中分离的化合物有:(1)2,2-二甲基环氧乙烷;(2)甲酸乙烯酯;(3)6-甲基双环[3,2,0]-庚-6-烯-2-酮;(4)6-丙基-双环[3,2,0]-庚-3,6-二烯-2-酮;(5)6-丙基-双环[3,2,0]-庚-6-烯-2-酮;(6)1,4-甲基奥,十氢-4,8,8-三甲基-9-亚甲基,(1s-(1α,3aβ,4α,8aβ)];(7)螺(5,5)=十一-2-烯-3,7,3,-三甲基-11-亚甲基(即β-chamigrene);(8)去氢喇叭醇;(9)榄香醇类似物等。     

超临界CO_2萃取和水蒸汽蒸馏法研究乌药中挥发性有机物

用超临界CO2萃取法(SFE-CO2)和水蒸汽蒸馏法(SD)对乌药中挥发性有机物进行提取,并运用GC-MS法分析了2种提取物中的化学成份。结果表明:SFE-CO2法提取物的产率为6.67%,SD法提取物的产率为0.60%;两种方法提得的乌药挥发性有机物中共鉴定出58个成分,其中SFE-CO2法和SD法提取物被鉴定的成分分别为46个和36个,共有成分24个,主要有柠檬烯、龙脑、龙脑乙酸酯、β-榄香烯、α-古云烯、桉叶4(14),11-二烯、δ-愈创木烯、4,4′-二甲基-2,2′-二亚甲基双环己基-3,3′-二烯、tau-杜松醇、β-桉叶油醇、8-甲基-2-苯基-4,7-二烯-2-壬醇、(2-[2-(2,4-二甲基苯基)环丙基]呋喃)等成分,占SFE-CO2法提取物被鉴定成分的54.56%,占SD法提取物被鉴定成分的78.42%。     

印度獐牙菜挥发油化学成分的研究

研究了印度獐牙菜(Swertia chitayita Buch-Ham．)挥发油的化学成分。采用水蒸气蒸馏法提取、毛细管气相色谱-质谱联用技术对印度獐牙菜挥发性化学成分进行了分离,经计算机质谱谱库检索对分离的化合物进行鉴定,并用已知烃类进行标定,共确定了其中63种化合物,所鉴定出的化合物含量占全挥发油的81．36％;用峰面积归一化法测定了各化学成分的相对含量。研究结果表明,印度獐牙菜的主要化学成分为：十六烷酸乙酯(19．54％)、4-(苯甲基)哌啶(11．72％)、油酸乙酯(7．82％)、丁基化羟基甲苯(6．70％)、亚油酸乙酯(5．80％)、丁二酸二乙酯(3．21％)、3a,6a-二氢-2(3H,4H)环戊二烯并[b]呋喃酮(2．13％)等。     

黄花补血草挥发性化学成分研究

为了研究黄花补血草挥发油的化学成分,本文采用了水蒸气蒸馏法从黄花补血草中提取挥发油,并用GC-MS法采用最佳分析条件对化学成分进行鉴定,用峰面积归一化法测定各化合物在挥发油中的相对百分含量;通过研究,鉴定出70种化合物,其峰面积相对含量约占挥发油总量82.12%。黄花补血草挥发油的主要组分为2-硝基乙醇(59.63%)、正二十四烷(3.71%)、二苯胺(2.31%)、6,10,14-三甲基-2-十五烷酮(1.79%)、正二十一烷(1.57%)、丙二醇(1.40%)等。     

Synthesis and anthelmintic activity of 7-substituted 3,4a-dimethyl-4a,5a,8a,8b-tetrahydro-6H-pyrrolo[3',4':4,5]furo[3,2-b]pyridine-6,8(7H)-diones

The racemic 7-substituted 3,4a-dimethyl-4a,5a,8a,8b-tetrahydro-6H-pyrrolo[3',4':4,5]furo[3,2-b]pyridine-6,8(7H)-diones represent novel tricyclic compounds with strong in vivo efficacy against the parasitic nematode Haemonchus contortus Rudolphi in sheep. Here we report on the synthesis of tricyclic endo-2,3-dihydro[3,2-b]pyridine-type cycloadducts and describe the separation of the racemic 3,4a-dimethyl-7-ethyl-4a,5a,8a,8b-tetrahydro-6H-pyrrolo[3',4':4,5]furo[3,2]pyridine-6,8(7H)-dione into the enantiomers by HPLC. The absolute configuration of the most anthelmintically active (4aS,5aS,8aS,8bR)-enantiomer was determined by single crystal X-ray analysis using its stable (4aS,5aS,8aS,8bR)-enantiomer-CuCl2 (2:1)-complex.     

Non-glycosidic iridoids from Cymbaria mongolica

Six non-glycosidic iridoids, i.e. (1R,4S,4aS,7S,7aS)-7-hydroxyl-4-hydroxy- methyl-7-methyl-1-methoxyl-1,4,4a,7a-tetrahydrocyclopenta[e]pyran-3-one (1), (1S,4R,4aS,7S,7aS)-7-hydroxyl-4-hydroxymethyl-7-methyl-1-methoxyl-1,4,4a,7a-tetrahydrocyclopenta[e]pyran-3-one (2), (1R,4R,4aS,7S,7aS)-7-hydroxyl-4-hydroxy-methyl-7-methyl-1-methoxyl-1,4,4a,7a-tetrahydrocyclopenta[e]pyran-3-one (3), (1R, 4R, 4aS, 7aS)-4,7-dihydroxymethyl-1-methoxyl-1,4,4a,7a-tetrahydrocyclopenta-6-ene[e]pyran-3-one (4), (1R, 4R, 4aS, 7aS)-4,7-dihydroxymethyl-1-hydroxyl-1,4,4a, 7a-tetrahydrocyclopenta-6-ene[e]pyran-3-one (5), (1R, 4S, 4aS, 7aS)-4,7-dihydroxy-methyl-1-methoxyl-1,4,4a,7a-tetrahydrocyclopenta-6-ene[e]pyran-3-one (6), as well as five known non-glycosidic iridoids mussaenin A (7), gardendiol (8), isoboonein (9), 4-epi-alyxialactone (10) and rehmaglutin D (11) have been isolated from the Chinese medicinal plant Cymbaria mongolica. Their structures were elucidated by spectroscopic methods. These compounds exhibit significant antitumor and antibacterial activity.     

Phenolic glycosides from Kaempferia parviflora

Three phenolic glycosides were isolated together with two known flavonol glycosides from the H2O-soluble fraction of rhizomes of Kaempferia parviflora. Their structures were determined to be rel-(5aS,10bS)-5a,10b-dihydro-1,3,5a,9-tetrahydroxy-8-methoxy-6H-benz[b]indeno[1,2-d]furan-6-one 5a-O-[alpha-L-rhamnopyranosyl-(1-->6)-beta-d-glucopyranoside] (1), its rel-5aS,10bR isomer (2), and (2R,3S,4S)-3-O-[alpha-L-rhamnopyranosyl-(1-->6)-beta-d-glucopyranosyl]-3'-O-methyl-ent-epicatechin-(2alpha-->O-->3,4alpha-->4)-(5aS,10bS)-5a,10b-dihydro-1,3,5a,9-tetrahydroxy-8-methoxy-6H-benz[b]indeno[1,2-d]furan-6-one 5a-O-[alpha-L-rhamnopyranosyl-(1-->6)-beta-D-glucopyranoside] (3). The structures were elucidated on the basis of analyses of chemical and spectroscopic evidence.     

藏药毛蕊杜鹃挥发油化学成分的GC-MS分析

目的：通过研究毛蕊杜鹃挥发油的化学成分,为毛蕊杜鹃的药用及开发利用提供依据.方法：采用水蒸气蒸馏法提取毛蕊杜鹃挥发油,用GC毛细管柱进行分离,归一化法测其相对含量,并用气相色谱-质谱法对化学成分进行鉴定.结果：共鉴定出38个化合物,鉴定出的化合物含量占总挥发油的92.96％.结论：毛蕊杜鹃挥发油主要成分为δ-杜松烯（相对含量为15.90％）;胡萝卜醇（15.09％）;α-杜松醇（15.02％）;τ-杜松醇（9.66％）;α-衣兰油烯（4.25％）;1,2,3,4,4a,5,6,8a-八氢-7-甲基-4-亚甲基-1-[1-甲基乙基]-萘（4.14％）;1,7-二甲基-4-异丙基-2,7-环癸二烯-1-羟基（3.27％）;石竹烯（2.86％）;5-甲基-9-亚甲基-2-异丙基-二环[4.4.0]癸-1-烯（2.62％）;1,4-二甲基-3-[2-甲基-1-丙烯-1-基]-4-乙烯基-1-环庚烯（2.42％）;γ-衣兰油烯（2.21％）;愈创醇（1.50％）;β-古芸烯（1.34％）.     

Synthesis of methyl dihydrohardwickiate and its C-4 epimer. Structural amendment of natural crolechinic acid

Reduction of the alpha, beta-unsaturated ester moiety of (+)-methyl hardwickiate with magnesium in methanol afforded methyl (4aS,6S,8aS,1R,5R)-5, 6,8a-trimethyl-5-[2'-(3"-oxoyl)-ethyl-perhydro-1-naphthalenyl]- carboxaylate, while reduction with sodium in n-propanol, followed by esterification with diazomethane, furnished its C-4 epimer. After comparison of the 1H- and 13C-NMR data of these compounds with those reported for crolechinic acid isolated from Croton lechleri, a stereochemical revision for the natural product is suggested.     

Studies on the synthesis of safflomin-A, a yellow pigment in safflower petals: oxidation of 3-C-beta-d-glucopyranosyl-5-methylphloroacetophenone

The direct C-glycosylation of methylphloroacetophenone 8 with d-glucose gave C-beta-d-glucopyranosylmethylphloroacetophenone (7) in 65% yield, which, on oxidation in the presence of small amount of pyridine under an oxygen atmosphere afforded the quinone 9, oxidized at the methylated position of the benzene ring as a pair of diastereomers in 27% yield. A detailed NMR analysis and a comparison of the UV-vis and CD spectra of their acetates indicated that the structure and stereochemistry of 9 was (1R,1'S,2R,3S,3aS,5R and 1R,1'S,2R,3S,3aS,5S)-7-acetyl-2-(1',2'-dihydroxyethyl)-5-methyl-3,5,6-trihydroxy-8-oxofuro[3,2-d]benzo[b]furan.     

Novel vasopressin V2 receptor-selective antagonists, pyrrolo[2,1-a]quinoxaline and pyrrolo[2,1-c][1,4]benzodiazepine derivatives.

The intent of the work was to study the structure-activity relationships of AVP receptor antagonists bearing a chiral ring as a partial structure since such studies had been reported for only achiral compounds. In the present paper, we deal with compounds consisting of the chiral tricyclic hetero ring (1,2,3,3a,4,5-hexahydropyrrolo[1,2-a]quinoxaline and 1,2,3,10,11,11a-hexahydro-1H-pyrrolo[2,1-c][1,4]benzodiazepine) and 2-phenylbenzanilide analogues. These compounds exhibited a highly selective affinity for V2 receptor, and their stereochemical configuration had a great influence on V2 receptor binding. VP-343 (N-[4-[[(2S,3aR)-2-hydroxy-2,3,3a,4-tetrahydropyrrolo[1,2-a] quinoxalin-5(1H)-yl]carbonyl]phenyl]-4'-methyl[1,1'-biphenyl]-2-ca rboxamide), VP-365 (N-[4-[[(11aS)-2,3,11,11a-tetrahydro-1H-pyrrolo[2,1-c][1,4]benz odiazepin-10(5H)-yl]carbonyl]phenyl][1,1'-biphenyl-2-carboxamide) and VP-339 (N-[4-[[(11aS)-5-oxo-2,3,11,11a-tetrahydro-1H-pyrrolo[2,1-c][1,4]+ ++benzodiazepin-10(5H)-yl]carbonyl]phenyl][1,1'-biphenyl]-2-carboxami de) were the most potent compounds in vitro and in vivo. The IC50 values of VP-343, VP-365 and VP-339 against V2 receptor were 0.772, 1.18 and 0.216 nM, respectively. The ED300 values (dose required to increase three times the urine volume of the control rats; oral administration) of VP-343, VP-365 and VP-339 were 0.22, 0.31 and 0.78 mg/kg, respectively.     

动态吸附与气相色谱-质谱（GC-MS）联用分析密蒙花（醉鱼草科）的挥发性花香成分

采用气相色谱-质谱联用技术对动态吸附法收集的密蒙花（Buddleja officinalis）花香成分进行了分析,并用气相色谱面积归-化法对各成分进行了定量。从密蒙花中分离出16个挥发性成分,定性定量出其中的11个,占挥发性成分总量的95．44％。其中丁基醋酸乙酯（81．57％）、苯甲醛（4．92％）、3-已烯-1-醇（3．26％）、欧洲丁香醛（2．34％）和芳樟醇（1．05％）为主要成分。该研究阐明了自然条件下密蒙花的花香成分及组成,其结果为今后定向创新醉鱼草属新香型观赏品种提供了科学依据。     

Characterisation and X-ray crystallography of products from the Bucherer-Bergs reaction of methyl 2,3-O-isopropylidene-alpha-D-lyxo-pentodialdo-1,4-furanoside

Methyl 2,3-O-isopropylidene-alpha-D-mannofuranosidurononitrile [alternative name: methyl (5R)-5-C-cyano-2,3-O-isopropylidene-alpha-D-lyxofuranoside] (2), methyl 2,3-O-isopropylidene-alpha-D-mannofuranosiduronamide [methyl (5S)-5-C-carbamoyl-2,3-O-isopropylidene-alpha-D-lyxofuranoside; methyl (5S)-2,3-O-isopropylidene-alpha-D-lyxo-hexofuranosiduronamide] (3), methyl 2,3-O-isopropylidene-alpha-D-mannofuranosiduronic acid [methyl (5S)-2,3-O-isopropylidene-alpha-D-lyxo-hexofuranosiduronic acid] (4), methyl 5-deoxy-2,3-O-isopropylidene-5-ureido-beta-L-gulofuranosiduronamide [methyl (5R)-5-deoxy-2,3-O-isopropylidene-5-ureido-alpha-D-lyxo-hexofuranosiduronamide (5), and (4S,5S,6R)-5,6-dihydro-6-hydroxy-4,5-isopropylidenedioxy-4H-pyrido[2,1-e]imidazolidine-2',4'-dione [IUPAC name: (3aS,4R,8aS)-4-hydroxy-2,2-dimethyl-3a,8a-dihydro-4H-1,3-dioxa-4a,6-diaza-s-indacene-5,7-dione] (6), instead of the expected hydantoin derivative, were obtained from the Bucherer-Bergs reaction of methyl 2,3-O-isopropylidene-alpha-D-lyxo-pentodialdo-1,4-furanoside (1). The structure of 6 was deduced from NMR and mass spectral data and confirmed by X-ray crystallography. The configuration at C-5 in 2-5 was confirmed by establishing the 5S configuration of 3 by X-ray crystallography. Conformations of the six- and five-membered rings in 3 and 6 are also discussed.     

Actinidia arguta: volatile compounds in fruit and flowers

More than 240 compounds were detected when the volatile components of the flowers and the fruit from several Actinidia arguta genotypes were investigated. Around 60-70 different compounds were extracted from individual tissues of each genotype. Two different methods of volatile sampling (headspace and solvent) favoured different classes of compounds, dependent upon their volatilities and solubilities in the flower or fruit matrices. The compounds extracted from flowers largely comprised linalool derivatives including the lilac aldehydes (12a-d) and alcohols (13a-d), 2,6-dimethyl-6-hydroxyocta-2,7-dienal (8), 8-hydroxylinalool (9), sesquiterpenes, and benzene compounds that are presumed metabolites of phenylalanine and tyrosine. Extracts of fruit samples contained some monoterpenes, but were dominated by esters such as ethyl butanoate, hexanoate, 2-methylbutanoate and 2-methylpropanoate, and by the aldehydes hexanal and hex-E2-enal. A number of unidentified compounds were also detected, including 8 from flowers that are so closely related that they are either isomers of one compound or two or more closely related compounds. This is the first report of the presence of a range of linalool derivatives in Actinidia.