含硫套索冠醚的合成

将二氮杂１８－冠－６的乙腈溶液分别与２－氯乙基烷基硫醚、２－氯乙基烯丙基硫醚、［２－（２－ｒ氯乙基）硫乙基］烷基硫醚在无水碳酸钾存在下反应制得５种新型侧链上含硫原子的双臂套索冠醚和５种新型单臂套索冠醚。它们的收率分别为３７％－７２％和１３％－３７％。此法比其它制备单臂套索冠醚的方法操作简单。     

Effects of metal salts on the thermal decomposition of edta-gel precursors for ferroelectric ceramic powders

Raw chemicals such as metal nitrates and chlorides were found to affect the thermal decomposition behaviour of EDTA-gel precursors used for the production of ceramic powders. Fine, homogeneous ceramic powders were produced from nitrate solutions while chlorides gave segregated phases. In studies on the production of lead zirconate titanate (PZT) using chlorides, the segregation and loss of lead was observed and shown to be caused by the formation and evaporation of PbCl₂. Thermal analysis (DTA/TG) quantitatively proved the suggested reaction mechanism for this phase segregation. Crystallization of the desired perovskite phase of lead zirconate titanate (PZT) and barium titanate (BT) initiated at temperatures as low as 250°C in the nitrate-EDTA precursors. Water of crystallization and formation of BaCO₃ in the barium titanate precursor were suggested to account for differences in the observed decompositional behaviours of the BT and PZT precursors.     

不对称诱导 Ⅱ.相转移催化下苯甲醛与氯仿、手性胺的反应

用溴化四正丁基铵作为相转移催化剂,苯甲醛、氯仿、α-苯基乙胺(la～c)和固体氢氧化钾在-5～0℃于无水乙腈中反应。反应产物2a～c经水解,氢解得到相应的光学活性苯甘氨酸(4a～c)。由1-苯基-2,2,2-三氯乙醇与1a反应也可制得2a,并对反应机理进行了讨论。     

Cyclization of 2,6-dialkoxy acetophenone hydrazones in the presence of polyphosphoric acid (PPA)

Cyclization of a series of 2,6-dialkoxy acetophenone hydrazones gave 3-methyl-4-alkoxyindazoles with elimination of the 2- or 6-alkoxy group in the presence of PPA. The reaction mechanism was discussed.     

双核Cu(Ⅱ)-2，4-二羟基苯甲醛缩邻氨基苯甲酸Schiff碱配合物的合成、表征和晶体结构

The novel dinuclear copper(Ⅱ) complex with with N-(2，4-dihydroxybenzalidene)-o-aminobenzoic acid ligand， [Cu(C₁₄H₉NO₄)]₂·2H₂O， has been synthesized and characterized by elemental analysis， IR， UV-Vis and thermal analysis. Its crystal structure was determined by single crystal X-ray diffraction techniques. The crystal belongs to monoclinic with space group P2₁/c. The cell parameters are: a=0.82510(11)nm， b=0.68870(9)nm， c=2.3007(3)nm， β=100.847(2)°， V=1.2840(3)nm³， Z=2，D_c=1.742Mg·m^-3， μ(Mo Kα)=1.723mm^-1， F(000)=684. The structure was refined to final R₁=0.0267， wR₂=0.0735. The complex molecule structure has dinuclear centrosymmetric dimeric structure in which a planar Cu₂O₂ core features. The ligand N-(2，4-dihydroxybenzalidene)-o-aminobenzoic acid dianion is μ₂-tridentate， chelating one copper(Ⅱ) ion via one nitro-gen， one hydroxy oxygen atom and one carboxylate oxygen atom， and the hydroxy oxygen atom simultaneously co-ordinates to the other copper(Ⅱ) ion of the dimer. In the structure the copper(Ⅱ) ion rendered four-coordination in a distorted square-planar geometry structure. CCDC: 212695.     

配合物Cu(C14H10N2O2)(C5H5N)的合成和晶体结构

The novel copper(Ⅱ) complex with salicylaldehyde benzoylhydrazone and pyridine ligands， Cu(C₁₄H₁₀N₂O₂)(C₅H₅N)， has been synthesized and characterized by elemental analysis， IR and thermal analysis. The crystal structure of the title complex has been determined by single crystal X-ray diffraction techniques. The crystal belongs to monoclinic with space group P2₁/c. The cell parameters are： a=1.6362(9)nm， b=1.7140(9)nm， c=1.2255(7)nm， β=105.168(9)°， V=3.317(3)nm³， Z=8， D_c=1.525g·cm^-3， μ(MoKα)=1.334mm^-1， F(000)=1560. The structure was refined to final R₁=0.0376， wR₂=0.0909. The copper(Ⅱ) ion lies in a dis-torted square-planar environment composed of two oxygen atoms， one nitrogen atom of tridentate acyhydrazone Schiff base ligand and one nitrogen atom of the pyridine ligand. CCDC： 193111.     

“黑洞型”缺电子联吡啶环蕃的合成

利用2,3,5,6-四氟-1,4-苯二甲酸为原料, 经过酯化、还原及溴代, 合成1,4-二溴甲基-2,3,5,6-四氟苯. 以其为原料在低温下利用模板效应合成高度缺电子的“黑洞型”缺电子联吡啶环蕃化合物, 经过连续液液萃取及离子交换得到“黑洞型”缺电子联吡啶环蕃单体. 产品经¹H NMR, ¹³C NMR, MS表征. 利用变温核磁共振技术研究“黑洞型”缺电子联吡啶环蕃与经典的双环(百草枯-对苯撑)型缺电子联吡啶环蕃在溶液中的变化.     

An Unexpected Discovery in the Willgerodt-Kindler Reaction of Acetophenone——the Formation of the 4-（Benzoylthiocarbonyl）morpholine

The Willgerodt-Kindler reaction of acetophenone was studied.Apart from the normal product 4-(benzylthio-carbonyl)morpholine,another product 4-(benzoylthiocarbonyl)morpholine was obtained unexpectedly.The struc-ture of the latter was confirmed by IR,~1H NMR spectra and X-ray diffraction analysis.The mechanism of the reac-tion was discussed.     

Establishment of heterodinuclear replacement complexation and its application to direct determination of iron in natural water with dibromo-o-nitrophenylfluorone

The chromophore dibromo-o-nitrophenylfluorone (DBNPF) was used to complex Fe(III) and Cu(II) at pH 5.88. Fe(III) can competitively replace Cu(II) from its dinuclear complex Cu(DBNPF)Cu, and forms the Cu(DBNPF)Fe heterodinuclear complex. The Fe-DBNPF and Cu-DBNPF complexes were also characterized by the spectral correction technique. The heterodinuclear replacement complexation (HRC) is proposed and first used for the quantitative detection of iron in trace level with high sensitivity and good selectivity by the light-absorption ratio variation approach. The limit of detection of Fe is 1.0 μg L⁻¹. The method has been successfully applied to the direct determination of Fe(II, III) dissolved and bound to suspended substances in natural water.     

卟吩垂直激发态的理论研究方法的比较

运用TDDFT、ZINDO、INDO/S三种量子化学理论方法,对卟吩的单线垂直激发态进行了理论计算与归属研究.研究发现,对于卟吩类大分子而言, ZINDO和INDO/S方法对研究Q带和B带等特征的低能量激发态具有足够的精度,且对高能带也能给出定性的解释,可以用于更大的生物发色团分子的垂直激发态的理论研究.