7-氨基-3-乙烯基头孢烷酸的合成

以7-苯乙酰氨基-3-氯甲基头孢烷酸对甲氧基苄酯为原料经Wittig反应、水解、酶解三步反应合成重要的药物中间体——7-氨基-3-乙烯基头孢烷酸,总收率71.2%。其结构经1H NMR和IR表征。     

密脉鹅掌柴中三萜类新化合物12α,13-二羟基齐墩果烷-3酮-28酸和新细胞周期抑制剂齐墩果酮酸

12α, 13-Dihydroxyolean-3-oxo-28-oic acid (1), a new pentacyclic triterpene, was isolated from Scheffiera venulosa (Wight et Am.) Harms through a bioassay-guided fractionafion procedure, together with the known oleanonic acid (2) as a new cell cycle inhibitor. Structures were estabfished by spectroscopy. Compound 2 inhibited the proliferation of K562 cells with the IC50 value of 0.13 lamol/mL by the SRB method and inhibited the cell cycle of tsFT210 cells at the G0/G1 phase at the concentration higher than 10 μg/mL.     

区别齐墩果-12-烯和乌苏-12-烯三萜的~13C NMR特征化学位移

齐墩果-12-烯(olean-12-ene)(Ⅰ)和乌苏-12-烯(urs-12-ene)(Ⅱ)型五环三萜的差别仅在于 E 环上甲基位置的不同。曾有多种光谱和     

2-卤-3-氨基-2-烯丙亚胺化合物的合成

由具有2位氢的3-氨基-2-烯丙亚胺与N-氯或N-溴琥珀酰亚胺以甲苯作溶剂在常温下反应，制备了-些未见文献报道的2-氯和2-溴-3-氨基-2-烯丙亚胺，化合物结构均经元素分析，^1H NMR，^13C NMR和MS确证。     

1-甲氧基-1-烷硫基丙烷的合成

甲氧基烷硫基丙烷;丙缩醛;硫醇;1-甲氧基-1-烷硫基丙烷的合成     

3,11(13)-二烯-12-桉烷酸的立体选择性全合成

桉烷型倍半萜类化合物广泛分布于天然植物中 ,此类化合物多具有较好的生理活性 ,其中桉烷酸类化合物因具有广泛的生物活性而受到重视 .例如 ,3,1 1 ( 1 3) -二烯 - 1 2 -桉烷酸 ( 1 )呈现较好的抗菌活性[1] ,桉烷酸 ( 2 )具有消炎退热的活性[2 ] . 3,1 1 ( 1 3) -二烯 - 1 2 -桉烷酸 ( 1 )是 Shtacher等 [1] 从地中海草药Inula viscosa Ait中分离得到的 .其合成工作尚未见文献报道 .化合物 ( 1 )和 ( 2 )的结构式见 Scheme1 .Scheme1　The structures of compouds1 and2首先以烯丙基氯化为关键反应 ,在桉烷骨架的 C- 1 2位上引入一个羟基…     

3-氨基-7,8-二甲氧基香豆素及其衍生物的合成及抗氧化活性

合成了3-氨基-7,8-二甲氧基香豆素及其衍生物共11个化合物,其中3个化合物(2b、2d、2e)为新型香豆素芳酰胺类化合物。 通过猝灭1,1-二苯基-2-三硝基苯肼(DPPH)、2,2'-联氮二(3-乙基苯并噻唑-6-磺酸)二铵盐阳离子自由基(ABTS^+·)和羟自由基实验考察了所合成化合物的抗氧化活性,结果表明化合物2b对DPPH自由基、羟自由基的清除能力超出或接近对照品维生素C,而衍生物2a、2b和2c的抗氧化活性优于母体。 故酰化可提高3-氨基-7,8-二甲氧基香豆素的抗氧化性能,尤其是普遍提高了羟基自由基的清除能力。     

3β-羟基-4,11-二烯桉烷酸甲酯的不对称全合成

近年来 ,从传统药用植物里分离出了很多桉烷酸类天然产物 ,它们绝大多数具有很好的杀菌、拒食等活性[1 ,2 ] .因此 ,对这一类天然产物的全合成研究成为当前的研究热点课题 .Ｓｃｈｅｍｅ 1　Ｔｈｅｓｔｒｕｃｔｕｒｅｏｆｃｏｍｐｏｕｎｄ 13β 羟基 4,1 1 二烯桉烷酸 (1 ,结构如Ｓｃｈｅｍｅ 1所示 )是德国化学家Ｂｏｈｌｍａｎｎ等[3] 从一种阿根廷的药用植物Ｓｔｅｖｉａａｃｈａｌｅｎｓｉｓ中分离得到的一个桉烷酸类天然产物 ,它的结构非常具有代表性 ,在反式十氢萘上共有 3个手性中心 ,其不对称全合成尚未见报道 .因此 ,如何高立体选…     

具有生物活性的紫檀芪和3’-甲氧基紫檀芪及其糖苷类化合物的合成

以3,5-二羟基苯甲酸、对羟基苯甲醛或香草醛为原料,以Wittig-Horner反应为关键步骤,合成了天然产物紫檀芪(1)和3’-甲氧基紫檀芪(2).以稀碱NaOH水溶液作缩合剂,四丁基溴化铵(TBAB)为相转移催化剂,使1和2在氯仿-水体系中分别与糖基供体α-溴代乙酰葡萄糖、乳糖和麦芽糖进行糖苷化反应,合成了一系列未见文献报道的紫檀芪和3’-甲氧基紫檀芪的糖苷类化合物3～10.所合成化合物的结构已由核磁共振谱、红外光谱和质谱所证实.并用MTT蛋白染色法对紫檀芪(1)和3’-甲氧基紫檀芪(2)进行了体外抗肿瘤细胞生物活性测试,发现其对HL-60(白血病细胞)、SMMC-7721(肝癌细胞)和SK-BR-3(乳腺癌细胞)三种肿瘤细胞均具有较好的细胞毒活性.     

3-芳烷氨基-6-氯哒嗪的合成及其除草活性

通过3,6-二氯哒嗪与(未)取代芳烷基胺在DMF/NaH或正丁醇体系缩合, 合成了13个3-芳甲(乙)氨基-6-氯哒嗪类化合物, 其中11个为新化合物, 它们的结构均经¹H NMR, IR和元素分析确证. 初步的生物活性测试结果表明, 所合成的化合物对阔叶杂草有一定的抑制作用, 如化合物4f在施药量为10 µg•mL^－1时对油菜的抑制率是76.42%. 讨论了其结构与除草活性的关系.     

24-亚甲基胆甾-5-烯-3β,19-二醇的合成

从豆甾醇出发,通过10步反应,合成得到具有显著细胞毒活性的24-亚甲基胆甾-5-烯-3β,19-二醇(1),总产率为16%.目标产物1的熔点、[α]值和波谱数据与天然产物一致.化合物1的合成是首次报道,它对人体鼻咽癌(CN2)和胃癌(Mgc803)细胞有显著抑制活性.     

Phytochemical,antimicrobial and antiquorum-sensing studies of pulicaria undulata L.: a revision on the structure of 1β,2α,3β,19α,23-pentahydroxy-urs-12-en-28-oic acid

Abstract

Phytochemical study of the aerial part of Pulicaria undulata L. led to the isolation of nine compounds. The structure of 1β,2α,3β,19α,23-pentahydroxy-urs-12-en-28-oic acid (4) was revised and confirmation of the stereochemical configuration of the hydroxyl groups was established using NOESY and selective decoupling experiments. The other compounds were identified as 1,2-dehydro-1,10α-dihydropseudoivalin (1), axillarin (2), grandifloric acid-15-β-glucoside (3), myrianthic acid (5), caffeic acid (6), quercetin (7), paniculoside IV (8) and caffeic anhydride (9). The structures were characterized by 1?D, 2?D NMR spectroscopy and confirmed with HRMS. Antimicrobial and antiquorum-sensing activities of the different extracts and isolated compounds of the plant were investigated. Generally, the phenolic rather than the terpenoidal compounds exhibited remarkable antimicrobial and antiquorum-sensing activity.

     

1H and 13C NMR Assignments for a 27-Norolean-13-en-3-hydroxy-28-oic Acid Glycoside from Isertiahaenkeana

A nortriterpene glycoside, pyrocincholic acid 3β-O-β-6-deoxy-D-glucopyranoside-28-O-β-D-glucopyranoside, was isolated from the leaves of Isertia haenkeana and its structure established by ¹H and ¹³C NMR spectral studies. The complete ¹H and ¹³C NMR resonance assignments for this triterpene were confirmed by the conventional 1D NMR methods and 2D shift-correlated NMR techniques: DQF COSY, TOCSY, ROESY and HMQC.     

(3E)-胆甾-4-烯-3,6-二酮-3-肟及其类似物的合成

以胆甾醇为原料,经氯铬酸吡啶氧化生成胆甾-4-烯-3,6-二酮(2),2与盐酸羟胺反应合成了(3E)-胆甾-4-烯-3,6-二酮-3-肟(3),总收率66%。利用合成3的反应条件合成了两个3的类似物——(3E)豆甾-4-烯-3,6-二酮-3-肟(6)和(3E)-谷甾-4-烯-3,6-二酮-3-肟(7)。2,3,6和7的结构经NMR和IR表征。     

Synthesis of 6E－Geranylgeraniol－19－oic Acid

The present paper deals with the facile synthesis of 6E-geranylgeraniol-19-oic acid(l), a naturally occuring alicyclic diterpene acid, by a Horner-Wadsworth-Emmons olefination of two readily available fragments 7 and 3.     

3-苯基-5-(1-环己烯)-2-戊烯-4-炔酸甲酯的合成

在PEG-400反应介质中,以PdCl2(PPh3)2/CuBr为催化体系合成了3-苯基-5-(1-环己烯)-2-戊烯-4-炔酸甲酯,该反应产率高,对环境友好,且催化体系可以适当地重复使用.     

3-甲基-1-戊烯-4-炔-3-醇的合成

以甲基乙烯酮为原料,用乙炔基格氏试剂对其加成,然后水解得到目标物3-甲基-1-戊烯-4-炔-3-醇。研究了温度对反应的影响,发现在25℃的反应温度下,目标化合物的气相色谱产率为50%,减压蒸馏纯化后收率为30%。目标产物用1HNMR、IR进行了表征。     

Synthesis of 4-amino-substituted but-2-en-4-olides

Previously unknown 4-amino derivatives of spiro-annelated Δ²-butenolide were synthesized by the addition of various amines at the activated triple bond of 4-hydroxy-2-alkynoic esters. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2761–2770, December, 2005.     

Oxidative cleavage of 3β-acetoxy-21-oxolup-18-en-28-oic acid by ruthenium tetroxide

3β-Acetoxy-21-oxolup-18-en-28-oic acid was used as a starting compound for oxidative cleavage by ruthenium tetroxide generated in situ from ruthenium dioxide by sodium metaperiodate in a biphasic system. Tricyclic and tetracyclic acids of baccharane type were prepared by this reaction, and their structures were confirmed using spectral data. These acids were further used for synthesis of appropriate methyl and acetoxymethyl esters. All prepared compounds were tested on cytotoxic activity against CEM tumor cell line, and several compounds showed activity in low micromolar concentrations.     

Two New Pentacyclic Triterpenes from Sabia parviflora

Two new pentacyclic triterpene acids,1α,3β-dihydroxyl-olean-12-en-28-oic acid and 1α，2α,3β-trihydroxyl-olean-12-en-28-oic acid, were isolated from the arial parts of Sabia parviflora.