SYNTHESIS OF SOLUBLE POLY（3,4-DIHYDROXY-o-TOLYLENE）： REDOX POLYMER

Conventional chloromethylation, paraformaldehyde/hydrogen chloride in acetic acid medium, was applied to 1,2- dimethoxybenzene. Chloroform-soluble poly（3,4-dimethoxy-o-tolylene） was obtained with an intrinsic viscosity of 0.034 dL g^-1. The polymer was evaluated as a condensation redox polymer precursor formed by a Friedel-Crafts reaction. Cleavage of the methoxy groups present in this polymer resulted in poly（3,4-dihydroxy-o-tolylene） which manifested a great air-oxidation resistance. The redox property of the latter polymer was found to be 1017 mV by potentiometric titration with 0.05 N ceric ammonium nitrate at 25℃. This midpotential was compared to that of catechol, a monomeric analogue, under the same titration conditions.     

｛[Co(4,4′-bipy)(ambdc)(H_2O)_2](4,4′-bipy)(DMF)｝_n合成与晶体结构

近年来,取代在5位上的间苯二甲酸(取代基为:-SO3H,-NH2,-OH,-NO2等)衍生物与过渡金属形成的配位聚合物,由于其具有新奇的结构,而且是潜在的功能材料而备受关注[1￣4]。Yaghi等人认为,取代基对配位聚合物的结构和性能具有重要的修饰作用[5]。因此我们在研究5-硝基间苯二甲酸、5-羟基间苯二甲酸与过渡金属形成的配位聚合物结构的同时[6,7],选择了5-氨基间苯二甲酸作为酸性配体,氨基不仅能用其氮原子与金属配位,还能形成氢键,能够提供丰富的配位方式。我们曾经报道了｛[Co(4,4′-bipy)(hmbdc)(H2O)2](4,4′-bipy)(DMF)｝n的合成与结构[8…     

CoAPO-11分子筛的合成、表征和催化性能： 1-己烯异构化反应

水热法合成了钴取代磷铝酸盐分子筛CoAPO-11，并采用了X射线衍射、扫描电子显微镜、红外光谱、紫外可见光谱以及氮气吸脱附等表征手段对合成的样品进行表征，并在合成的分子筛上进行1-己烯异构化反应评价，并考查了温度和空速对反应的影响。结果表明，在反应温度300℃及空速为2.4h－1CoAPO-11分子筛对1-己烯异构化反应具有较好的催化性能。     

C19-二萜生物碱贡乌生的结构研究

毛茛科植物贡嘎乌头 ( Aconitum liljestrandii)具有镇痛、镇静、祛风湿等功效 ,产于我国西藏东部及四川西部 [1] .我们从其块根中分得 1 8个单体 ,其中 1 6个为已知生物碱 [2 ,3] ,2个为新生物碱 [3] .本文报道新的 C19-二萜生物碱贡乌生 ( Liljestrandisine) 1的结构 .1　实验部分1 .1　仪器与试剂　 Boetius微量熔点测定仪 ;Nicolet FTIR2 0 0 SXV型红外光谱仪 ,KBr压片 ;BrukerAC- E2 0 0和 Varian Unity INOVA40 0 /5 4核磁共振仪 ,溶剂为 CDCl3,TMS为内标 ;VG Autospec30 0 0型和 VG70 A型质谱仪 ;Pekin Polarimete…     

A Novel Reductive Cyclization of o-Nitrobenzamides and Ketones Promoted by Low-valent Titanium Reagent

A short and facile synthesis of a series of 1,2-dihydroquiazolin-4(3H)-ones was accomplished in good yields via novel reductive cyclization of o-nitrobenzamides with ketones promoted by TiCI4/Zn system. The structure was established on the basis of elemental analysis, IR,^1H NMR and confirmed by a single-crystal X-ray diffraction analysis. This method has the advantages of easily accessible starting materials, convenient manipulation and moderate to high yields.     

镉(Ⅱ)与对苯二甲酸和2,2′-联吡啶配合物光谱性质的理论研究

对镉(Ⅱ)与对苯二甲酸和2,2′-联吡啶配合物进行几何优化,在优化构型的基础上分析了其吸收光谱.结果表明主要贡献的激发态为16,17和26激发态而不是第一激发态,振子强度f为0.2052,0.3202和0.3234,对应的吸收波长为308.57,307.33和258.35 nm,与实验值310和253 nm相近.     

β-环糊精与二苯胺超分子包合物

研究了β-环糊精(主体)与二苯胺(客体)的包合反应。通过元素分析、核磁共振、差热分析及X-射线粉末分析方法确定了包合物的形成，用荧光光谱法测定了包合反应的形成常数。实验结果表明：β-环糊精与二苯胺分子形成摩尔比为2∶1的包合物。二苯胺的苯环嵌入β-环糊精分子的疏水性空腔内。包合物的分子式为C₉₆H₁₅₁O₇₀N。热稳定性比相应主客体明显提高。     

α-单取代环十二酮肟及缩氨基硫脲的合成及晶体结构

单晶X射线衍射分析表明, α-单取代环十二酮与氨衍生物羟胺和氨基硫脲发生缩合反应得到两种母体构象均为[3333], 而取代基为边外向或角反向的α-单取代环十二酮肟或缩氨基硫脲. 利用底物的“角位羰基参与反应”原理, “记忆效应”及进攻试剂与底物是否形成氢键解释了这一实验结果. 通常情况下, 试剂从空间障碍小的一面进攻羰基而生成α-角反取代环十二酮肟或缩氨基硫脲. 当试剂与底物的取代基之间能够形成分子间氢键时, 则生成α-边外取代环十二酮肟或缩氨基硫脲.     

立体专一性地合成（Z）-α-氟-β-三氟甲基乙烯基碘化物和应用于合成多氟噻吩基双烯烃

The direct iodination of polyfluorinated vinyl stannanes by tin-iodine exchange methodology was achieved giving （Z）-α-fluoro-β-trifluoromethyl vinyl iodides stereospecifically. Changing the substituent in R group from the electron-withdrawing group to electron-donating group led to an increase in the yield from 78% to 90%, while it was moved from para to meta position the reaction did not afford a dramatic change in the yield （90% to 95%）. In addition, this reaction also can be applied to the vinyl stannane with heterocyclic group. The further coupling reaction of prepared vinyl iodide containing heterocyclic moiety with （Z）-α-fluoro-β-trifluoromethylstannanes gave polyfluorinated heterocyclic alkadienes with 2E,4E-selectivity.     

可控制自由基聚合DPE法制备P(AA-MMA-ST)/Fe3O4磁性复合微球

在制备超细Fe₃O₄磁性粒子的基础上, 利用可控制自由基聚合DPE法制备出平均粒径为265 nm的P(AA-MMA-ST)/Fe₃O₄磁性复合微球. 采用XRD, TGA, FTIR等手段对所制备的磁性复合微球的形态、结构及磁响应性等进行了表征, 结果表明用DPE法制备出的磁性复合微球磁含量较高, 粒径比较均匀.