N-芳基氮氧方酸的合成研究

N-芳基氮氧方酸(3-芳胺基-4-羟基-3-环丁烯二酮)是合成不对称方酸衍生物的关键中间体之一，开展了对其合成方法的研究，发现并实现了方酸与芳伯胺在水中的脱水反应，制得17个N-芳基氮氧方酸3a～3q，其中N-8'-喹啉基氮氧方酸(3q)具有热致变色性质，根据实验事实，提出了可能的反应历程。该合成方法产率较高，产物易于分离纯化，是制备N-芳基氮氧方酸简便有效的好方法。     

1,3-二-(3,3-二甲基-2-甲烯假吲哚)方酸菁染料的合成及其晶体

合成了两个新型方酸菁染料3和5。在酸催化下,2,3,3-三甲基假吲哚不需N-烷基化,可直接与方酸反应。反应过程中发生了明显的质子转移。结晶学数据表明,分子3的整体位于同一平面;溶剂苯规则地排布在方酸四碳环的周围,后者酷似电子陷阱。染料5有良好的水溶性。     

一些新的磺胺衍生物的合成研究

众所周知，大多数磺胺用于治疗各种疾病，结构奇特的方酸具有特定的功能。我们成功地将磺胺结构单元引入方酸四碳环，制得14个新的含方酰基的磺胺衍生物，确证了结构。预期这类化合物有新的生物活性。     

Novel Fluorene-based Conjugated Copolymer Containing Cyclobutenedione Unit for Light Emitting Diodes

A novel fluorene-based conjugated copolymer containing cyclobutenedione unit was synthesized by Suzuki reaction.Its structure and properties were characterized by FTIR,^1HNMR,elemental analysis,PL spectroscopy,DSC,TGA and cyclic voltammetry.The resulting polymer shows strong yellow PL emission(561nm)and good solubility in polar aprotic solvents,i.e.THF,DMF,DMAC,DMSO,etc.DSC and TGA studies reveal that the novel polymer possesses excellent thermal stability with high glass transition temperature of 127℃ and onset decomposition temperature of 411℃.Cyclic voltammetry measurement demonstrated that the polymer has both hole and electron-transporting property.     

Synthesis and Antiplasmodial Activity of Bisindolylcyclobutenediones

Malaria is one of the most dangerous infectious diseases. Because the causative Plasmodium parasites have developed resistances against virtually all established antimalarial drugs, novel antiplasmodial agents are required. In order to target plasmodial kinases, novel N-unsubstituted bisindolylcyclobutenediones were designed as analogs to the kinase inhibitory bisindolylmaleimides. Molecular docking experiments produced favorable poses of the unsubstituted bisindolylcyclobutenedione in the ATP binding pocket of various plasmodial protein kinases. The synthesis of the title compounds was accomplished by sequential Friedel-Crafts acylation procedures. In vitro screening of the new compounds against transgenic NF54-luc P. falciparum parasites revealed a set of derivatives with submicromolar activity, of which some displayed a reasonable selectivity profile against a human cell line. Although the molecular docking studies suggested the plasmodial protein kinase PfGSK-3 as the putative biological target, the title compounds failed to inhibit the isolated enzyme in vitro. As selective submicromolar antiplasmodial agents, the N-unsubstituted bisindolylcyclobutenediones are promising starting structures in the search for antimalarial drugs, albeit for a rational development, the biological target addressed by these compounds has yet to be identified.     

双臂型方酰胺多齿配体的合成(三)

1,3-取代方酰胺内鎓盐分子中,二氧环丁烯结构单元上的氧相与富电,应有较好的配位能力。Maneke和Gauger虽然注意到这一点,但有关研究仍不多。为有效利用二氧环丁烯上氧的配位性,在其邻近的空间合理地配置齿形结构的配位链,以协调和加强分子的配位功能,改善配     

Diphosphine ring expansion and π-bond reduction in the reaction between 1,2-bis(diphenylphosphino) cyclobutenedione (bpcbd) and Ru3(CO)10(MeCN)2: X-ray diffraction structures of Ru3(CO)10[2,3- bis(diphenylphosphino)succinic anhydride] and Ru2(CO)6(bma)

Replacement of the acetonitrile ligands in Ru₃(CO)₁₀(MeCN)₂ by the diphosphine ligand 1,2-bis(diphenylphosphino)cyclobutenedione (bpcbd) initially gives the unstable bpcbd-bridged cluster Ru₃(CO)₁₀(bpcbd) (1), followed by its subsequent transformation to the triruthenium cluster Ru₃(CO)₁₀(bma) (2). The decomposition of cluster 2 serves to produce the ruthenium compounds Ru₃(CO)₁₀[2,3-bis(diphenylphosphino)succinic anhydride] (3) and Ru₂(CO)₆(bma) (4). Compounds 2–4 provide the experimental evidence for the ring expansion of the cyclobutenedione ring via the formal insertion of an oxygen atom into the four-membered ring and hydrogen addition to the bond upon exposure to the atmosphere and/or moisture. Both 3 and 4 have been isolated and characterized in solution by IR and ³1P NMR spectroscopies, and the molecular structure of each product has been verified by X-ray crystallography. Ru₃(CO)₁₀[2,3-bis(diphenylphosphino)succinic anhydride] crystallizes, as the CH₂Cl₂ solvate, in the monoclinic space group P2₁/c, a = 12.178(2)Å, b = 15.988(2)Å, c = 22.472(3)Å, = 95.115(2)°, V = 4358(1)ų, Z = 4, and d_calc = 1.732 Mg/m³; R = 0.0344, R_w = 0.0931 for 5683 reflections with I > 2(I). The dinuclear compound Ru₂(CO)₆(bma) crystallizes in the triclinic space group P-1, a = 9.298(3)Å, b = 12.020(3)Å, c = 30.858(8)Å, = 81.774(5)°, = 89.276(5)°, = 83.545(4)°, V = 3391(1)ų, Z = 4, and d_calc = 1.730 Mg/m³; R = 0.0670, R_w = 0.1444 for 8766 reflections with I > 2a(I).     

含磺酰胺基和羧苯基的异方酰胺的合成

以3-[邻(或对)羧苯胺基]-4-羟基-3-环丁烯二酮(1a, 1b)为底物,与一些磺胺反应, 成功地制得了14个新的不对称取代的异方酰胺。3a～3f和4a～4f结构上的共同特点是, 有药物作用的磺酰胺和邻(或对)氨基苯甲酸的结构单元, 通过方酸四碳环的桥接作用而共存于同一分子之中。     

芳基异方酰胺与HMPA及一些羧酰胺的反应

研究了1,3-双芳基异方酰胺与六甲基磷酰三胺(HMPA)及其它羧酰胺的反应制得了15个既含芳胺基又含脂肪基的不对称方酰胺。该反应提供了制备既含芳胺基又含二甲胺基、甲胺基和乙胺基的不对称方酰胺的较为有效的方法。对反应机理作了初步讨论。     

方酸与某些偶氮化合物的反应

作为非苯系芳香性化合物和有机插烯二元酸,双功能性的方酸,可与许多亲核试剂反应并生成相应的双取代产物,通常都很难生成单取代产物。当它与芳环直接相连时会产生惊人的深色位移,这类化合物有诱人的应用前景。考虑到偶氮染料在染料工业中的作用和地位,我们试图在方酸衍生物中引入偶氮基,