新型苯并吡喃黄酮的合成及其抗肿瘤活性

2,2-二甲基-8-乙酰基-7-羟基-5-甲氧基色满分别与对甲基苯甲酰氯,间氯苯甲酰氯和间三氟甲基苯甲酰氯经Baker-Venkataraman重排和关环反应合成了3个新型的苯并吡喃黄酮(3a~3c);1-(2″,4″-二甲氧基苯基)-3-(2',2'-二甲基-7'-羟基-5'-甲氧基色满-8')-1,3-二酮(4)分别与烯丙基溴,异戊烯基溴和碘甲烷经取代和关环反应合成了3个新型的3-烃基苯并吡喃黄酮(6a~6c)。3和6的结构经1H NMR,13C NMR和MS表征。采用MTT法和SRB法研究了3和6体外对人白血病细胞(K562)和人肺癌细胞(K549)的抗肿瘤活性。结果表明:2',4'-二甲氧基-2″,2″-二甲基-3″,4″-2H二氢吡喃-3-甲基-5″,6″:5,6-黄酮(6c)显示了较好的抗肿瘤活性。     

(±)-2-甲基-5-羟基-2-(4'-甲基-3'-戊烯基)-二氢-1-苯并吡喃黄烷酮的全合成

以2,4,6-三羟基苯乙酮和柠檬醛为起始原料,经环化、保护酚羟基、羟醛缩合、脱保护、催化环化等反应以5.9%的总产率完成了天然产物(±)-2-甲基-5-羟基-2-(4'-甲基-3'-戊烯基)-二氢-1-苯并吡喃黄烷酮的全合成,其结构经1H NMR,13C NMR和HR-ESI-MS确证。     

两种天然异戊烯基黄烷酮的全合成

以3-甲氧基甲氧基苯甲醛和2,4,6-三甲氧基-3-异戊烯基苯乙酮为原料,经烷基化和缩合反应合成了新化合物——2’-羟基-4-甲氧基-3,4’,6’-三甲氧甲氧基-3’-异戊烯基査尓酮(6);6经环合反应合成了新化合物——(±)-5,7,3’-三甲氧甲氧基-4’-甲氧基-8-异戊烯基黄烷酮(7);7经脱保护和环合反应实现了天然产物(±)-5,7,3’-三羟基-4’-甲氧基-8-异戊烯基-黄烷酮(1,总收率11.6%)和(±)-5,3’-二羟基-7,8-(2,2-二甲基吡喃)-4’-甲氧基黄烷酮(2,总收率10.5%)的全合成,其中1为新化合物,其结构经1H NMR,IR和MS表征。     

Paratocarpin B的全合成

以对羟基苯甲醛和2,4-二羟基苯乙酮为起始原料,经过C-异戊烯基化、保护酚羟基、羟醛缩合、催化环化、去保护基等反应,以18.4％的总收率首次完成了天然异戊烯基查尔酮Paratocarpin B的全合成,中间体3′,4′-(2,2-二甲基吡喃)-2′-羟基-3-异戊烯基-4-甲氧甲氧基查尔酮(10)未见文献报导,其结构经1H NMR,IR和MS表征.     

新型螺双二氢茚二酚衍生物的合成

螺双二氢茚二酚(SPINOL)与N-溴代丁二酰亚胺经溴代反应制得6,6'-二溴-螺双二氢茚二酚(1);1与叔丁基二甲基硅基三氟甲磺酸(TBSOTf)经醚化反应得6,6'-二溴-7-羟基-7'-叔丁基二甲硅氧基-1,1'-螺二氢茚(2);SPINOL经羟基保护后与碘甲烷经双甲基化反应制得6,6'-二甲基-7,7'-双(1-甲氧甲氧基)-1,1'-螺二氢茚(4);4经脱保护后再与TBSOTf经醚化反应合成了6,6'-二甲基-7-羟基-7'-叔丁基二甲硅氧基-1,1'-螺二氢茚(6)。2和6为新化合物,其结构经1H NMR,13C NMR和HR-ESI-MS表征。     

8-异戊烯基黄酮类天然产物的微波促进Claisen重排合成

8-异戊烯基黄酮是一类具有显著生物活性的天然产物.以2,4,6-三羟基苯乙酮和3,4-二羟基苯甲醛为原料,用氯甲基甲醚保护羟基,经羟醛缩合、碘催化环合、过氧丙酮(DMDO)氧化、O-异戊烯基化、微波促进的Claisen重排、脱甲氧甲基保护基、O-甲基化和异戊烯基侧链环合等反应步骤,完成了8-异戊烯基槲皮素-3-甲醚(1)、8-异戊烯基槲皮素-3,7,3',4'-四甲醚(2)和ArtochaminC(3)这3种8-异戊烯基黄酮类天然产物的合成.并对由微波促进的由5-O-异戊烯基黄酮类化合物合成8-C-异戊烯基黄酮类化合物的Claisen重排反应的关键步骤进行了探讨.所有合成的化合物经~1H NMR、~(13)C NMR和MS等结构确证.     

(±) Cudraflavanone B及(±)-5-O-Methyl Cudraflavanone B的全合成研究

以2,4,6-三羟基苯乙酮和2,4-二羟基苯甲醛为起始原料, 经过异戊烯基取代、选择性保护羟基、Mitsunobu反应、Claisen重排、醛酮缩合、催化环化及去保护基等步骤, 首次完成了天然异戊烯基黄烷酮Cudraflavanone B的全合成, 同时也完成了(±)-5-O-甲基-6-(2"-异戊烯基)-7,2',4'-三羟基黄烷酮的全合成研究.     

新型蒎烷基吡唑酰胺类衍生物的合成及其生物活性研究

以诺蒎酮为原料,合成了新型蒎烷基吡唑酰胺类衍生物,并对其生物活性进行了研究.诺蒎酮与芳香醛进行缩合反应,得到中间体3-芳亚甲基诺蒎酮2a~2g,2a~2g与水合肼经环化、脱氢芳构化反应,得到新型蒎烷基吡唑类化合物3a~3g;以N,N-二甲基甲酰胺为溶剂,3a~3g与2-氯乙酰胺在碱催化作用下,合成了7种吡唑酰胺类化合物4a~4g.其结构经~1H NMR,~(13)C NMR,IR,和HRMS表征.通过X射线衍射分析测定了化合物2-(6',6'-二甲基-3'-(4'-甲氧基苯基)-4',5',6',7'-四氢-5',7'-桥亚甲基-吲唑-1'-基)乙酰胺(4d)的晶体结构.探讨了化合物3a~3g和4a~4g的抑菌活性和对蚜虫的杀虫活性.实验结果表明,2-(6',6'-二甲基-3'-(4'-氟苯基)-4',5',6',7'-四氢-5',7'-桥亚甲基-吲唑-1'-基)乙酰胺(4g)既具有较好的抑菌效果,同时对紫薇蚜虫也表现出较好的杀虫活性.     

环丙鱼藤双腙的合成与抑菌活性

以鱼藤酮为原料,经氧硫叶立德开环、环合,再与水合肼缩合制备关键中间体(2R)-5-[5',6'-二甲氧基-1',1'a,2',7'b-四氢环丙并[c]苯并吡喃-7'b-基)(亚联氨基)甲基]-2-(丙烯-2'-基)-2,3-二氢苯并呋喃-4-酚(2),2与多种醛/酮反应,合成16个结构新颖的环丙鱼藤双腙化合物3a~3p,结构经1H NMR和LRMS确证.初步抑菌活性测试表明,鱼藤双腙化合物对稻纹枯病菌、油菜菌核病菌和小麦白粉病菌的抑制率/防治率较高.其中化合物3d和3o在500 mg/L浓度下对稻纹枯病菌的防治率分别为55.1%和55.5%;化合物3a,3c,3e,3h和3k在25 mg/L浓度下对油菜菌核病菌的抑制率分别为76.8%,87.0%,70.6%,72.5%和65.2%;化合物3a,3c,3g,3i和3l在500 mg/L浓度下对小麦白粉病菌的防治率为80.0%~90.0%.     

尼达尼布的合成新方法

以N-甲基-4-硝基苯胺作为起始原料,依次经氯乙酰化、取代及氢化还原反应制得关键中间体N-(4-氨基苯基)-甲基-2-(4-甲基-1-哌嗪基)乙酰胺（4）;以4-氯-3-硝基苯甲酸为原料,依次经酯化、取代、氢化还原及环合反应制得6-甲氧羰基-2-吲哚酮（8）; 8与原苯甲酸三乙酯和乙酸酐经“一锅煮”反应制得中间体1-乙酰基-3-甲氧基(苯基)亚甲烯基-2-氧代吲哚环-6-羧酸甲酯（9）; 4和9进行取代反应的同时脱除保护,经“一锅煮”反应合成尼达尼布,总收率57.2%,其结构经¹H NMR,¹³C NMR和MS(ESI)确证。     

TOTAL SYNTHESIS OF(±)LESPEDEZAFLAVANONE-A

Lespedezaflavanone-A(1)was a new isoprene substituted flavanone which was isolated from, the root bark of Lespedeza davidii.In this paper, the total synthesis of its racemate(±)-1 was reported.     

First Total Synthesis of the (±)-Preverecynarmin

The preverecynarmin(12), (+)-(1E,3E,7E,11E)-cembra-3,7,11-tetraen-6yl acetate,was first isolated in 1990 from both Armina maculata and its prey,the pennatulacean coral Veretillum cynomorium with other there briarane diferpenoids and cembene-C((1E,3E,7E,11E)-cembra-l,3,7,11-tetraen¹. As far as we known, the bioactive test and total synthesis of ¹² have not been reported yet. Herein we wish to describe the first total synthesis of (±)-preverecynarmin (12).     

The Total Synthesis of (±)-13-Hydroxyneocembrene

(13S)-hydroxyneocembrene(18), a cembranoid which was isolated in 1988 from soft coral Sarcophyton trocheliophorum¹, has been shown to be an effective inductor of the release of labeled glucose from the lecithincholesterol liposomes and have cytostatic activities². The geometrical structure and absolute configuration of 18 have been defined to be 1S, 2E, 7E, 11E, 13S. Herein, we report the total synthesis of (±)-13hydroxyneocembrene(18).     

石松属生物碱Sieboldine A的全合成研究进展

简要介绍了石松属生物碱Sieboldine A的分离、生物活性及结构特征,综述了目前国内外对于Sieboldine A的全合成研究进展,详细论述了各个实验组在引入羟胺缩醛结构及构建cis-6/5稠环体系所采取的不同策略,并介绍了一价金催化的串联烯炔环化反应、路易斯酸催化的semipinacol重排和二碘化钐引发的自由基Pinacol偶联反应在Sieboldine A全合成中的应用。     

Facile Synthesis of (±)-2,6-Dimethethyl-6-hydroxy-2,7-octadienoic Acid and its Methyl Ester and Amide (Acacialactam)

The monoterpenoid acid 1, which is a component of some traditional medicine such as Gymnocladus chinensis baillon in glycoside form,¹ was recently isolated from Artemisia sieberi in Iran in free form.². Its structure has been established to be (E)-2,6-dimethyl-6-hydroxy-2,7-octadienoic acid (1) by chemical and spectroscopic analysis. Its methyl ester derivative 2,was isolated from the antibacterial extracts of the leaves of Piper aduncum³ as well. Acacialactam, a natural product isolated from the seeds of Acacia concinna DC.(Legunninosae) used in folk medicine of several tropical countries for treating some skin diseases, was assigned structure 4 by Sekine et al⁴ on the basis of its physical and spectral properties.     

Production of no-carrier-added 177Lu via the 176Yb(n, &;#947;)177Yb &;#8594; 177Lu process

No-carrier-added ¹⁷⁷Lu was produced by the ¹⁷⁶Yb(n,)¹⁷⁷Yb¹⁷⁷Lu process using enriched ¹⁷⁶Yb₂O₃. The radiochemical separation of the nca ¹⁷⁷Lu from the macroscopic ytterbium target was investigated by reversed-phase ion-pair HPLC. Effects of the concentrations of 2-hydroxyisobutyric acid and 1-octanesulfonate in the eluent, the amount of Yb₂O₃, the type and length of the C₁₈ column on the separation efficiency were examined. Under optimum conditions, the nca ¹⁷⁷Lu was obtained in radiochemically pure form from 5 mg of Yb₂O₃ with a separation yield of 84%.     

Enantioselective Resolution of (±)-l-Phenylethyl Acetate by Using the Whole Cells of Deep-sea Bacterium Bacillus sp. DL-2

Bacillus sp. DL-2 was isolated from the deep sea of the Western Pacific and further utilized as novel biocatalysts to efficiently asymmetrically hydrolyze (±)-1-phenylethyl acetate. After the optimization of hydrolytic reactions, chiral chemicals (R)1-phenylethanol and (S)-l-phenylethyl acetate were obtained with high optical purities (96% and 99.8%, respectively). Our research is about the asymmeric hydrolysis of (±)-1-phenylethyl acetate using whole-cell biocatalysts. In addition, the optical purity of (S)-l-phenylethyl acetate generated through the kinetic resolution of (±)-1-phenylethyl acetate using the whole-cells of Bacillus sp. DL-2 was the highest report so far. Using the whole cells of deep sea bacterium Bacillus sp. DL-2 as the biocatalysts is an enviromnentally friendly method and will play critical roles in industrial asymmetric synthesis.     

Comments on “Physicochemical Properties and Spectral Studies for Binary Systems of 2-Ethoxyethanol (1) + Water (2) and + Dimethyl Sulfoxide (2)”

The activation Gibbs energies, activation enthalpies and activation entropies reported by the authors were found to be internally inconsistent. Errors were also found in the numerical values of the Redlich–Kister equation coefficients for describing the excess molar volumes and viscosity deviations of both binary systems studied by the authors.     

Solid–Liquid Phase Equilibria in the Ternary Systems (LiBO 2 + NaBO 2 + H 2 O) and (LiBO 2 + KBO 2 + H 2 O) at 288.15 K and 0.1 MPa

Solid–liquid phase equilibria for the two aqueous systems (LiBO2 + NaBO2 + H2O) and (LiBO2 + KBO2 + H2O) at T = 288.15 K and p = 0.1 MPa were determined using the isothermal dissolution equilibrium method. The experimental results show that the phase diagrams consist of one two-salt co-saturated invariant point, two univariant solubility isotherms, and three crystallization fields. The two systems belong to simple co-saturated type, and neither double salt nor solid solution were found. The densities change regularly as the sodium metaborate (potassium metaborate) concentration increases in solution, and reach their maximum values at the invariant point. Based on the Pitzer and its extended Harvie–Møller–Weare (HMW) model, the solubilities for the ternary systems at 288.15 K were represented, and the calculated results agree well with the experimental values.     

(S)-5,5'-二氨基-2,2'-双二苯基膦基-1,1'-联萘的绿色合成

以2,2'-双二苯基磷基-1,1'-联萘[(S)-1]为原料,与H2O2经氧化反应制得(S)-2,2'-双二苯基磷氧基-1,1'-联萘[(S)-2];(S)-2经酸性树脂催化硝化制得(S)-5,5'-二硝基-2,2'-双二苯基磷氧基-1,1'-联萘[(S)-3)];(S)-3经Pd/C催化硝基氢化还原制得(S)-5,5'-二氨基-2,2'-双二苯基磷氧基-1,1'-联萘[(S)-4];(S)-4经HSi Cl3/PPh3还原制得(S)-5,5'-二氨基-2,2'-双二苯基膦基-1,1'-联萘,总产率65.6%,其结构经1H NMR,31P NMR和IR确证。