茜草中新化学成分的研究

<正> 首次自茜草(Rubia cordifolia L.)中分离得到文献未见报道的新化合物6-羟基-2H-萘骈〔1,2-b〕吡喃-2-酮-5-羧酸甲酯。作者从茜草的乙醇提取物的氯仿萃取部分中用硅胶柱层析分离得到一单体,通过理化常数测定、紫外、红外光谱、~1H-NMR、~(13)C-NMR光谱、质谱分析及衍生物的制备,确定该化合物为6-羟基-2H-萘骈〔1-2-b〕吡喃-2-酮-5-羧酸甲酯。     

胡椒属植物脚Piper rusbyi叶中杀利什曼原虫的成分

以生物活性为导向,从胡椒属植物Piper rusbyi C.DC.分离到具抗利什曼原虫活性最强的成分(+)-(7R,8S)-环氧-5,6-二脱氢醉椒素(1)和黄醉椒素(2),还分得1个新的卡瓦吡喃酮(7R,8R)-或(7S,8s)-二羟基-5,6-二脱氢醉椒素(3)和4个已知化合物。检测了它们抗利什曼原虫的活性。     

马尾松松针中木脂素类成分的分离与鉴定

目的研究松科植物马尾松(Pinus massoniana Lamb.)松针的化学成分。方法利用色谱技术分离纯化,根据化合物的理化性质和光谱数据进行结构鉴定。结果从马尾松松针水煎液的正丁醇部位分离得到3个化合物,分别鉴定为:(7S,8R)-3′,4,9′-三羟基-4-甲氧基-9-O-莽草酰基-7,8-二氢苯并呋喃-1′-丙基新木脂素(massonianoid A,I),(7S,8R)-4,9,9′-三羟基-3,3′-二甲氧基-7,8-二氢苯并呋喃-1′-丙基新木脂素(II),4,4′,8-三羟基-4,4′-二甲氧基-9-木脂内酯(III)。结论化合物I为新化合物,II和III为首次从本植物中分离得到。     

3-芳基-6-(溴代芳甲基)-7H-噻唑并[3,2-b]-1,2,4-三嗪-7-酮类化合物的设计、合成及其乙酰胆碱酯酶抑制活性研究

目的设计合成3-芳基-6-(溴代芳甲基)-7H-噻唑并[3,2-b]-1,2,4-三嗪-7-酮类化合物,并探讨C-6位芳甲基上引入溴原子对其乙酰胆碱酯酶抑制活性的影响。方法以4-羟基苯甲醛为原料,经溴代反应,得到3-溴-4-羟基苯甲醛和3,5-二溴-4-羟基苯甲醛,再将溴代的4-羟基苯甲醛与乙酰甘氨酸经Erlenmeyer-Plchl反应、水解反应、缩合反应合成目标化合物3-芳基-6-(溴代芳甲基)-7H-噻唑并[3,2-b]-1,2,4-三嗪-7-酮类化合物。采用Ellman法对目标化合物进行体外乙酰胆碱酯酶抑制活性筛选。结果所有目标化合物的结构均经红外光谱、质谱和核磁共振氢谱确证。目标化合物经体外乙酰胆碱酯酶抑制活性筛选,结果显示:所有目标化合物均具有乙酰胆碱酯酶抑制活性,其中8个化合物在10μmol.L-1浓度水平抑制活性超过了40%。结论在7H-噻唑并[3,2-b]-1,2,4-三嗪-7-酮类化合物母核C-6位芳甲基中引入溴原子的3-芳基-6-(溴代芳甲基)-7H-噻唑并[3,2-b]-1,2,4-三嗪-7-酮类化合物普遍具有较高的AChE抑制活性,并且引入2个溴原子的化合物抑制活性明显高于引入1个溴原子的化合物。     

铁刀木中一个新的色酮苷

目的 研究铁刀木的化学成分。方法 利用硅胶柱色谱和薄层色谱分离铁刀木的化学成分,通过理化常数测定和波谱分析等鉴定化合物的结构。结果从铁刀木树干中分离并鉴定了5个化合物,其结构分别鉴定为:β-谷甾醇(I),蔗糖(II),正二十八醇(III),2-甲基-5-(2′-羟丙基)-7-羟基色酮-2′-O-β-D-吡喃葡糖苷(IV),3,3′,4,5′-四羟基二苯乙烯(V)。结论化合物II,III,V为首次从该植物中分得,化合物IV为新化合物。     

决明子中萘骈吡喃酮类衍生物的分离与鉴定

目的研究决明子(Cassia obtusifolia L.)的化学成分。方法综合运用多种色谱学分离手段进行分离纯化,根据化合物波谱学数据对其结构进行鉴定。结果从决明子中共分离得到5个化合物,分别鉴定为2-甲基-5,10-二羟基-8-甲氧基-4H-萘[1,2-b]吡喃-4-酮-10-O-β-D-吡喃葡萄糖基-(1→3)-O-β-D-吡喃葡萄糖基-(1→6)-O-β-D-吡喃葡萄糖苷(1)、demethylflavasperone gentiobioside(2)、去甲基红镰霉素-6-O-β-D-吡喃葡萄糖苷(3)、去甲基红镰霉素-6-O-β-D-(6'-O-乙酰基)吡喃葡萄糖苷(4)、nor-rubrofusarin gentiobioside(5)。结论化合物1为新化合物。     

3-(氨基烷氧基芳基)-7H-噻唑并[3,2-b]-1,2,4-三嗪-7-酮类化合物的设计、合成与乙酰胆碱酯酶抑制活性

目的初步探讨在7H-噻唑并[3,2-b]-1,2,4-三嗪-7-酮类化合物母核C-3位苯环侧链中引入二乙胺基团的3-(氨基烷氧基芳基)-7H-噻唑并[3,2-b]-1,2,4-三嗪-7-酮类化合物的合成及其乙酰胆碱酯酶抑制活性。方法以取代的苯甲醛和乙酰甘氨酸为初始原料,经Erlenmeyer-Plchl反应、缩合反应、水解反应、缩合反应,生成6-芳甲基-3-硫代-1,2,4-三嗪-5(2H)-酮类化合物,再与取代的α-氯代苯乙酮反应,得到6-芳甲基-3-(羟基芳基)-7H-噻唑并[3,2-b]-1,2,4-三嗪-7-酮类化合物;以芳基乙烯为原料,经温和的氧化反应、缩合反应得到3,4-二氢-6-芳基-3-硫代-1,2,4-三嗪-5(2H)-酮类化合物,再与取代的α-氯代苯乙酮在乙酸中反应得到6-芳基-3-(羟基芳基)-7H-噻唑并[3,2-b]-1,2,4-三嗪-7-酮类化合物。两条合成路线得到的3-(羟基芳基)-7H-噻唑并[3,2-b]-1,2,4-三嗪-7-酮类化合物进一步经Williamson反应制备得到10个3-(烷氧基芳基)-7H-噻唑并[3,2-b]-1,2,4-三嗪-7-酮类化合物。所有目标化合物结构均经质谱、红外光谱和核磁共振氢谱确证。采用Ellman法对目标化合物进行体外乙酰胆碱酯酶抑制活性筛选。结果根据前期已筛选化合物的活性数据和总结出的初步构效关系,设计并合成了10个C-3位苯环侧链中含有二乙胺基团的3-(氨基烷氧基芳基)-7H-噻唑并[3,2-b]-1,2,4-三嗪-7-酮类化合物。体外乙酰胆碱酯酶抑制活性筛选表明,所有目标化合物均具有乙酰胆碱酯酶抑制活性,其中7个化合物在10μmol.L-1浓度水平抑制活性超过了50%。结论根据体外重组人源AChE(rhAChE)抑制活性的测试结果,发现C-3位苯环侧链中含有二乙胺基团的7H-噻唑并[3,2-b]-1,2,4-三嗪-7-酮类化合物均具有较好的rh-AChE抑制活性。在这一位置的侧链中引入二乙胺基团,可以增强化合物对rhAChE的抑制活性。     

蔓性千斤拔化学成分研究

从豆科植物蔓性千斤拔Flemingia phi-lippinensis(Merret Rolfe)Li的根部分离到13个化合物,分别经光谱及化学方法予以鉴定。其中4个新的黄酮类化合物,命名为蔓性千斤拔素甲(Flemiphilippinin A,晶Ⅵ)、蔓性千斤拔素乙(晶Ⅶ)、蔓性千斤拔素丙(晶Ⅺ)和蔓性千斤拔素丁(晶Ⅻ)。蔓性千斤拔素乙、丙和丁的结构分别确定为5,7,4’-三羟基-3’-甲氧基-6,8-双异戊烯基异黄酮,7-(4’-羟基-3’-甲氧基苯基)-5-羟基-2,2-二甲基-10-异戊烯基-2H,6H-苯骈-[1,2-b:5,4-b’]二吡喃6-酮和5,7,2’,4’-四羟基-6,8-双异戊烯基双氢黄酮。蔓性千斤拔素甲的化     

番石榴叶的化学成分

目的研究番石榴叶的化学成分。方法运用多种色谱技术方法对番石榴叶的化学成分进行了系统的研究,并根据波谱数据和理化性质确定了其结构。结果分离鉴定了7个化合物,分别为槲皮素-3-O-α-L-吡喃阿拉伯糖苷(quercetin-3-O-α-L-arabinopyranoside,1)、槲皮素-3-O-α-L-呋喃阿拉伯糖苷(quercetin-3-O-α-L-arabinofuranoside,2)、槲皮素-3-O-β-D-吡喃半乳糖(quercetin-3-O-β-Dgalactopyanoside,3)、2α,3β-二羟基乌索烷(2α,3β-di-hydroxy-ursane,4)、madecassic acid(5)、(7R,8S)二氢脱氢二松柏醇-9-O-β-D-吡喃葡萄糖苷((7S,8R)-5-methoxydehydrodiconiferyl alcohol-9-β-D-glucopyranoside,6)、quadranoside III(7)。结论化合物4-7为首次从番石榴属中分离得到。     

瑞舒伐他汀钙有关物质的合成

为控制瑞舒伐他汀钙的质量,制备了瑞舒伐他汀钙的5个有关物质：[(3R,5S,E)-7-[4-(4-氟苯基)-2-[[2-[4-(4-氟苯基)-6-异丙基-2-[N-甲基(甲基磺酰胺基)]嘧啶-5-基]-2-羟基乙基]-N-甲基磺酰胺基]-6-异丙基嘧啶-5-基]-3,5-二羟基庚-6-烯酸酯]钙盐(有关物质A)、[(3R,5S,E)-7-[4-(4-氟苯基)-2-[[(E)-2-[4-(4-氟苯基)-6-异丙基-2-[N-甲基(甲基磺酰胺基)]嘧啶-5-基]乙烯基]-N-甲基磺酰胺基]-6-异丙基嘧啶-5-基]-3,5-二羟基庚-6-烯酸酯]钙盐(有关物质B)、N-[4-(4-氟苯基)-5-[(E)-2-[(2R,4R)-4-羟基-6-氧代四氢-2H-吡喃-2-基]乙烯基]-6-异丙基嘧啶-2-基]-N-甲基甲磺酰胺(有关物质C)、N-[(R)-8-氟-6-[(2S,4R)-4-羟基-6-氧代四氢-2H-吡喃-2-基]-4-异丙基-5,6-二氢苯并[h]-喹唑啉-2-基]-N-甲基甲磺酰胺(有关物质D)、N-[(S)-8-氟-6-[(2S,4R)-4-羟基-6-氧代四氢-2H-吡喃-2...     

Thiophene systems. 14. Synthesis and antihypertensive activity of novel 7-(cyclic amido)-6-hydroxythieno[3,2-b]pyrans and related compounds as new potassium channel activators.

The synthesis and antihypertensive activity of novel 7-(cyclic amido)-6-hydroxy-5,5-dimethylthieno[3,2-b]pyrans and related compounds are described. The compounds were tested for oral antihypertensive activity in spontaneously hypertensive rats (SHR) and selected compounds were evaluated in vitro for increases in 86Rb efflux in rabbit isolated mesenteric arteries. The effects on activity in SHR of lactam ring size, the presence of heteroatoms in the lactam ring, the relative stereochemistry at C-6 and C-7, and the substituents on the thiophene ring are examined. The best racemic compound in this series is 32, trans-5,6-dihydro-6-hydroxy-5,5-dimethyl-2-nitro-7-(2-oxopiperidin -1-yl)-5H- thieno[3,2-b]pyran, which is 10-fold more potent than cromakalim with an ED30 = 0.015 mg/kg in SHR. Compound 32 could be resolved and the antihypertensive activity determined to reside primarily in the (6S,7S)-(-)-enantiomer 41. Surprisingly, the elimination of water to give the enamides 50-52, thiophene isosteres of bimakalim, diminishes activity significantly.     

杜仲叶中倍半萜及降碳倍半萜的分离与鉴定

目的 研究植物杜仲(Eucommia ulmoides Oliver)叶中的化学成分.方法 综合运用硅胶柱色谱、反相硅胶柱色谱和Sephadex LH-20凝胶柱色谱以及制备型高效液相色谱等方法进行系统分离,根据化合物的理化性质及其波谱数据确定化合物的结构.结果 从杜仲叶80％(体积分数)乙醇提取物中分离得到了12个倍...     

泰国产攀援鱼藤的异黄酮苷成分

目的： 对泰国产攀援鱼藤［Derris scandens (Roxb.) Benth］地上部分的化学成分进行分离、鉴定。方法： 采用各种层析色谱技术进行分离。从攀援鱼藤中分离得到2个化合物,用IR,UV,MS,¹HNMR,¹³CNMR,²DNMR光谱鉴定化合物。结果： 经光谱鉴定化合物结构为： 4′-甲氧基－异黄酮-7-O-［α-L-鼠李吡喃糖基(1→6)］-β-D-葡萄吡喃糖苷(I)和4′,8-二甲氧基-异黄酮-7-O-［α-L-鼠李吡喃糖基(1→6)］-β-D-葡萄吡喃糖苷(II), 分别命名为攀援鱼藤苷甲(derriscanoside A)和攀援鱼藤苷乙(derriscanoside B)。结论： 化合物(I), (II)为新的异黄酮苷类化合物。     

荷叶中化学成分的分离与鉴定

目的研究荷叶中的化学成分。方法采用正相硅胶、反相ODS、Sephadex LH-20等柱色谱及PHPLC法进行分离纯化,并通过理化性质、光谱分析方法及与文献对比,鉴定化合物的化学结构。结果从荷叶体积分数为70%的乙醇提取物中分离鉴定了8个化合物,其中有4个木脂素类:(+)-松脂醇[(+)-pinoresinol,1]、(+)-表松脂醇[(+)-epipinoresinol,2]、sylvatesmin(3)、(+)-异落叶松树脂醇[(+)-isolariciresinol,4];4个降倍半萜类:(3S,5R,6S,7E)-5,6-epoxy-3-hydroxy-7-me-gastigmen-9-one(5)、4,5-dihydroblumenol A(6)、(E)-3-oxo-retro-α-ionol(7)、(3S,5R,6R,7E,9S)-megastigman-7-ene-3,5,6,9-tetraol(8)。结论化合物1-8均为首次从莲属植物中分离得到。     

脚骨脆的化学成分研究

目的研究脚骨脆小枝和叶的化学成分。方法采用乙醇提取,提取物经萃取后以硅胶、凝胶和MCI等柱色谱法及高效液相色谱法进行分离纯化,采用波谱法进行结构鉴定。结果从该植物共分离得到8个化合物,其结构鉴定为:(6R,7E,9R)-9-hydroxymegastigm-4,7-dien-3-one,(6S,7E)-6-hydroxy-4,7-megastig-madiene-3,9-dione,(3S,5R,6S,7E)-5,6-epoxy-3-hydroxymegastigm-7-en-9-one,(6E,9S)-9-hydroxymegastigm-4,6-dien-3-one,caseamembrin A,casearlucin B,β-谷甾醇和胡萝卜苷。结论前6种化合物为首次从该植物中分离得到。     

Zur Totalsynthese des 5-Acetoxy-6-methoxykawains

Total Synthesis of 5-Acetoxy-6-methoxykawain The oxidation of 5-hydroxy-4-methoxy-6-trans-styryl-2H-pyran-2-one ( 6 ) by periodic acid in methanol gives rise to racem.-4,6-dimethoxy-6-trans-styryl-2,5-pyrandione ( 7 ). The yield is 35% Compound 7 is the key intermediate¹⁾ for the total synthesis of (5S, 6S)-(+)-acetoxy-4,6-dimethoxy-6-trans-styryl-5,6-dihydro-2H-pyran-2-one ( 1 ).     

Indole alkaloids of Odyendea gabonensis

From the trunk bark of Odyendea gabonensis six indole alkaloids have been isolated: Canthin-6-one (I); 5-Methoxy-canthin-6-one (II); 4,5-Dimethoxycanthin-6-one (III); 8-Hydroxy-canthin-6-one (IV); 1-Hydroxy-methyl-beta-carboline (V); and 1-Carboxamide-beta-carboline (VI). This is the first report of these products from this plant.     

Indole Alkaloids of Odyendea gabonensis.]

From the trunk bark of ODYENDEA GABONENSIS six indole alkaloids have been isolated: Canthin-6-one (I); 5-Methoxy-canthin-6-one (II); 4,5-Dimethoxycanthin-6-one (III); 8-Hydroxy-canthin-6-one (IV); 1-Hydroxy-methyl-beta-carboline (V); and 1-Carboxamide-beta-carboline (VI). This is the first report of these products from this plant.     

Norsesquiterpenoid glucosides and a rhamnoside of pyrrolizidine alkaloid from Tephroseris kirilowii

Four new glycosylated compounds have been isolated from the whole plant of Tephroseris kirilowii, including (-)-(1R,5R,6S,7R,8S)-8-O-beta-D-glucopyranosyloxy-7-hydroxy-6-(2-hydroxypropan-2-yl)-9-methylenebicyclo[4.3.0]non-3-one (tephroside A, 1), (-)-(1R,5R,6R,8R)-6-(2-O-beta-D-glucopyranosyloxypropan-2-yl)-8-hydroxy-9-methylenebicyclo[4.3.0]non-3-one (tephroside B, 2), thesinine-4'-O-alpha-L-rhamnoside (3), and p-coumaric acid 4-O-alpha-L-rhamnoside (4), together with the known roseoside. The structures of the new compounds were established by means of spectroscopic analysis.     

Novel diarylheptanoids of Alpinia blepharocalyx

The seeds of Alpinia blepharocalyx K. Schum. (Zingiberaceae) is used in Chinese traditional medicine for the treatment of stomach disorders. From the ether fraction of a 95% ethanolic extract, which showed hepatoprotective and antiproliferative activities, we isolated 16 novel diarylheptanoids bearing a chalcone or a flavanone moiety [calyxins A-H; epicalyxins B-D, G, and H; 6-hydroxycalyxin F; and blepharocalyxins A and B] together with seven known compounds, while the residual fraction of the ethanolic extract gave 32 novel diarylheptanoids namely, calyxins A, E-G, and I-M; epicalyxins B, F, I-K, and M; deoxycalyxin A; blepharocalyxins C-E; neocalyxins A and B; (3S,5S)- and (3S,5R)-3-hydroxy-1-(4-hydroxyphenyl)-5-methoxy-7-phenyl-6E-heptene, (3S,5S)- and (3S,5R)-3-hydroxy-1-(4-hydroxyphenyl)-5-ethoxy-7-phenyl-6E-heptene, (3S)-3-methoxy-1,7-bis(4-hydroxyphenyl)-6E-hepten-5-one, 1,7-bis(4-hydroxyphenyl)-hepta-4E,6E-dien-3-one, (3S,7R)-5,6-dehydro-1,7-bis(4-hydroxy-phenyl)-4"-de-O-methyl-centrolobine, (3S,5S,6S,7R)-5,6-dihydroxy-1,7-bis(4-hydroxyphenyl)-4"-de-O-me-thylcentrolobine, (3S,5R,6S,7R)- and (3S,5S,6R,7R)-5,6-dihydroxy-1,7-bis(4-hydroxyphenyl)-4"-de-O-methyl-centrolobine, 1,2- dihydro-bis(de-O-methyl)curcumin, and (3S,7S)-5,6-dehydro-4"-de-O-methylcentrolobine, and one known diarylheptanoid [(3S,5S)-3,5-dihydroxy-1,7-bis(4-hydroxyphenyl)heptane] together with 12 other known phenolic compounds. Moreover, in vitro NO inhibitory and antiproliferative activities of the isolated compounds were also tested and the active constituents identified.