新型香豆素类Mannich碱荧光功能化合物的合成及性质研究

以4-卤代间苯二酚为原料经甲酰化反应合成了2,4-二羟基-5-卤代苯甲醛,再通过Knoevenagel缩合反应合成了5种香豆素衍生物,最后经Mannich反应获得了5种未见文献报道的香豆素类荧光功能化合物.所得的荧光化合物的结构均用1H NMR,IR,MS和元素分析等方法进行了表征,并且对该类化合物的荧光性质及对金属离子的响应进行了研究.结果发现,由于光诱导电子转移(PET)的作用,在Mannich反应后,目标产物的荧光强度弱于反应前,而当该产物与金属离子配合后,PET作用减弱,荧光强度得到恢复.     

超声膜扩散法制备纳米银粒子

采用超声膜扩散(Ultrasound-assisted reaction method, UAMR)的方法, 以NaBH4还原溶液中的银离子, 在聚乙烯吡咯烷酮(PVP)为稳定剂的条件下, 制备出了平均粒度为4.7 nm的银纳米粒子. 与超声滴加法(Ultrasound-assisted dropping reaction method, UADR)相比, 超声膜扩散法制备出来的银纳米粒子的粒径小, 且尺寸分布较窄.     

Synthesis of alpha,alpha-dibromo esters as precursors of ynolates

Aliphatic alpha,alpha-dibromo esters, precursors of ynolates, were synthesized via bromination of lithium alpha-bromo ester enolates with 1,2-dibromotetrafluoroethane in good yields. alpha-Trimethylsilyl-alpha,alpha-dibromo esters were synthesized via radical bromination.     

各种烯基锆化合物的合成及其在立体选择性合成二(三)取代的烯烃中的应用

烯基锆化合物及硒基烯基锆化合物、锡基烯基锆化合物、磺酰基烯基锆化合物、亚磺酰基烯基锆化合物、硅基烯基锆化合物等金属或杂原子取代的烯基锆化合物 ,可通过锆氢化反应高产率和高选择性地制得 .这些试剂可与各种亲电试剂反应立体选择性地合成二取代或三取代的烯烃化合物     

Indium-mediated formation of propargyl ketones from aldehydes or acyl chlorides

Propargyl ketones were prepared from aldehydes via an indium-mediated alkynylation reaction followed by an indium-mediated Oppenauer oxidation. They were also obtained via an indium-mediated alkynylation of the relevant acyl chlorides.     

Synthesis of 3-aminoindole derivatives: combination of Thorpe-Ziegler cyclization and unexpected allylindium-mediated decyanation

α-Anilinonitriles were unexpectedly converted to 3-iminodihydroindoles via the Thorpe-Ziegler cyclization during the benzoylation. 3-Iminodihydroindoles were transformed to 3-aminoindoles in good yields via an allylindium-mediated decyanative aromatization.     

奥拉西坦衍生物的设计、合成及抗血小板聚集活性研究

本文采用拼合策略,设计、合成了7个新型奥拉西坦衍生物。其中,化合物4a～4f由奥拉西坦与苯丙烯酸片段拼合得到; 4g则由奥拉西坦、吲哚布芬拼合得到。采用Bron比浊法测定目标化合物对花生四烯酸及二磷酸腺苷诱导的血小板聚集的抑制活性。结果表明,该系列化合物具有一定的抗血小板聚集活性,其中化合物4f的抗血小板聚集活性与阳性对照吲哚布芬相当。     

带有酰胺侧基的中空手性高分子微球的合成及其分离性能

合成了带有手性基团的多孔高分子微球, 并将其作为高效液相色谱手性固定相用于分离制备盐酸贝那普利的一个重要中间体(R)-α-羟基苯丁酸乙酯.     

A direct route to isoflavan quinones. The synthesis of colutequinones A and B

The first syntheses of colutequinone A and colutequinone B were achieved. Radical generation via phenyliodoso diacetate was superior to radical generation via ammonium persulfate.     

One-Pot Wittig and Knoevenagel Reactions in Ionic Liquid as Convenient Methods for the Synthesis of Coumarin Derivatives

Efficient synthesis of a variety of 3-substituted coumarins via NaOMe-catalyzed Knoevenagel condensation and one-pot preparation of 3,4-unsubstituted coumarins in the presence of NaOMe via Wittig reaction in room-temperature ionic liquids are described. Knoevenagel condensation of 2-hydroxybenzaldehyde with dimethyl- and diethylmalonate was performed with excellent yields in room-temperature ionic liquids. Although diethyl- and dimethylchloromalonates were mostly recovered unchanged in Knoevenagel condensation, higher conversions were observed via Wittig reaction of these compounds with 2-hydroxybenzaldehyde derivatives and triphenylphosphine. Other 2-hydroxybenzaldehyde derivatives, methyl- and ethylchloroacetates, were reacted in ionic liquids to afford simple coumarins in good yields. These reactions widen the applicability of ionic liquid in organic synthesis.     

Photochemical structuring and fixing of structures in binary polymer brush layers via 2pi+2pi photodimerization

Binary polymer brushes grafted to Si wafers were prepared from hydrophilic and hydrophobic polymer components, which allow switching the surface properties (as revealed by contact angles) by exposure to varying solvents. The hydrophilic component was poly-2-vinylpyridine; the hydrophobic component was a copolymer of styrene and 2-(4-vinylphenyl)indene containing the photodimerizable phenylindene chromophore. The brushes were prepared via thermal and via photochemical grafting-to methods, which led to distinct layer thicknesses. Structural patterns differing in surface properties were produced and fixed via crosslinking the hydrophobic component by 2pi+2pi photodimerization of phenylindene moieties. The patterns were visually observable.     

Synthesis and antibacterial activity of novel 10, 11-epoxy acylide erythromycin derivatives

A series of novel acylide derivatives have been synthesized from clarithromycin A via a facile procedure. The C-3 modifications involved replacing the natural C-3 cladinosyl group in clarithromycin core with different aryl-piperzine sidechain via chemical synthesis. Meanwhile a distinctive intermediate with 10,11-epoxy moiety was obtained. The structure and stereochemistry of this novel structure were confirmed via NMR and X-ray crystallography. Potential anti-bacterial activities against both Grampositive and Gram-negative bacteria were reported. Because of existence of C10,11-epoxide, these derivatives can be used as intermediates for further structural modification.     

正丙醇诱导合成WO3粉体与光致变色性质

采用正丙醇为有机诱导剂, 在水热条件下制备了形貌新颖的WO3粉体, 使用XRD, SEM和TEM等手段进行了结构和形貌表征, 并用紫外-可见(UV-Vis)光谱仪及测色计测试了光致变色性能. 结果表明, 正丙醇诱导合成的WO3粉体仍为六方相, 但形成了特殊的海胆状纳米结构, SEM和TEM测试结果表明, 海胆状WO3微球由大量的WO3纳米杆簇集形成. 该诱导产物的纳米杆簇集成的海胆状结构显著地改善了光生质子的传输过程, 提高了合成的WO3粉体的光致变色性能.     

Pd-mediated synthesis of 2-arylquinolines and tetrahydropyridines from modified Baylis-Hillman adducts

We synthesized 2-arylquinolines and tetrahydropyridines via palladium-mediated Heck type reactions starting from the Baylis-Hillman adducts. 2-Arylquinolines were prepared via the Heck type cyclization followed by concomitant aerobic oxidation.     

Three different dimerizations of 2-bromo-3-methyl-1,4-naphthoquinones

Three types of dimeric naphthoquinones, which possess structurally diverse skeletons, can be prepared in one step from 2-bromo-3-methyl-1,4-naphthoquinones. 2,2'-Dimeric naphthoquinones were prepared by a one-pot Stille-type reaction via vinylstannanes. Oxepines are formed by unexpected domino reactions via 1,4-dihydroxynaphthalene species. Epoxides are formed by a Michael/Darzens reaction via the o-quinone methides.     

Construction of Thioamide Peptides from Chiral Amino Acids

Thioamide peptides were synthesized in a straightforward one-pot process via the linkage of diverse natural amino acids in the presence of thiolphosphonate and trichlorosilane, wherein carbonyl groups were replaced with thiono compounds with minimal racemization. Experimental and computational mechanistic studies demonstrated that the trichlorosilane enables the activation of carboxylic acids via intense interactions with the Si−O bond, followed by coupling of the carboxylic acids with thiolphosphonate to obtain the key intermediate S-acyl dithiophosphate. Silyl-activated quadrangular metathesis transition states afforded the thioamide peptides. The potential applications of these thioamide peptides were further highlighted via late-stage linkages of diverse natural products and pharmaceutical drugs and the thioamide moiety.     

Synthesis of the stereoisomers of 17,21-dimethylheptatriacontane - sex recognition pheromone of the tsetse fly

The title compounds were obtained both by application of directed resolution via diastereomeric amides and a novel asymmetric synthesis via ester enolates.     

Emulsion procedures for thermally reversible covalent crosslinking of polymers

Quaternization and dequaternization of tertiary amine compounds were employed to obtain thermally reversible ionene networks from aqueous colloidal polymer dispersions prepared via emulsion polymerization. Chlorine‐functionalized polymers prepared via the emulsion copolymerization of styrene (St), butylacrylate (BA), or both with chloromethylstyrene, and amino‐functionalized polymers prepared via the emulsion copolymerization of St, BA, or both with 2‐(dimethylamino)ethylacrylate or 4‐vinylpyridine, were reacted without polymer separation, with a ditertiaryamine crosslinker and a dihalide crosslinker, respectively, to obtain crosslinked polymers. Crosslinked polymers were also obtained via the reaction of a chlorine‐functionalized polymer dispersion with an amino‐functionalized polymer dispersion or via the drying of the polymer blend prepared from the two kinds of dispersions. Reactive solubility experiments, flowability investigations (by thermocompression at ca. 215 °C), IR, and ¹H NMR analyses of the obtained crosslinked polymers indicated that the generated ionene bridges dequaternized on heating and requaternized on cooling. In comparison with solution crosslinking, no organic solvent was employed, and simple procedures were required for the preparation of the thermally reversible covalent crosslinked polymers. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4373–4384, 2000     

A Synthetic Approach to Homologous Blockcopolymers

Summary: Blockcopolymers of 3-methyl-3-phenylcyclopropene and norbornene derivatives were synthesized via ROMP. The crossover reaction during ROMP blockcopolymerization was successfully monitored via MALDI-TOF MS in agreement with GPC and NMR-methods.     

Development and application of patterned conducting polymer thin films as chemoresponsive and electrochemically responsive optical diffraction gratings

We describe the preparation of two-dimensionally patterned polyaniline (PANI) thin films via microtransfer molding and electropolymerization techniques. This procedure yields reproducible conducting polymer patterns with excellent feature periodicity, making them useful as diffraction gratings. The fabricated polymer gratings were characterized via tapping-mode atomic force microscopy. Spectroelectrochemistry was used to characterize the optical properties associated with various intrinsic PANI redox states. In accordance with the Kramers–Kronig relation for change-in-absorptivity and change-in-index-of-refraction, electrochemically induced changes in refractive index (detected via changes in diffraction efficiency) were observed to coincide with electrochemically-induced changes in the PANI electronic absorption spectrum. In addition, the higher oxidation states of PANI and the associated changes in refractive index proved accessible via chemical oxidation. Beyond the novelty of a chemically-switchable transmission grating, the response of this system points to the possibility of developing diffraction-based chemical sensing schemes.