含吗啉基片段的水杨醛席夫碱类化合物的合成及其淬灭1,1-二苯基-2-三硝基苯肼自由基性能

通过3-氟-4-吗啉基苯胺和取代水杨醛缩合反应,合成了14个含吗啉基片段水杨醛席夫碱类化合物(Ⅰa-Ⅰn)。通过核磁共振波谱仪(NMR)、傅里叶变换红外光谱仪(FTIR)、液相色谱-质谱联用仪(LC-MS)和元素分析等技术手段研究了产物的结构和淬灭1,1-二苯基-2-三硝基苯肼(DPPH)自由基的活性。 结果表明,在0.02~0.10 g/L,所有化合物均表现出一定的淬灭DPPH自由基活性。 其中,化合物Ⅰd和Ⅰf表现出较为优异的性能,化合物Ⅰd的活性在30%~55%,化合物Ⅰf的活性则大于50%。 随着化合物Ⅰd、Ⅰh、Ⅰj和Ⅰn质量浓度的增大,其淬灭DPPH自由基的活性均呈现增强趋势。     

Sharpless四唑合成中捕获双四唑锌配合物

The reaction of malononitrile with ZnCl₂ and NaN₃ in the presence of 2,2′-bipyridine and water affords the first bis(tetrazole) Zn-complex intermediate, mono(2,2′-bipyridine)bis(tetrazolyl)methane aqua zinc(Ⅱ), [Zn(2,2′-bpy)(BTZ)(H₂O)]·(H₂O)₂ (1) which gives a clue for Demko-Sharpless′ tetrazole synthesis. Crystal data for 1: C₁₃H₁₈N₁₀O₄Zn, M_r=443.74, monoclinic, space group P2₁/c, a=12.5705(18), b=16.078(2), c=9.1921(13)?, β=95.010(3)°, V=1850.7(5)?³, Z=4. CCDC: 197788.     

α-单取代环十二酮构象的研究

利用分子力学计算，单晶X射线分析和~1H NMR技术研究了α-单取代环十二酮 的构象。结果表明，它们的优势构象的环骨架仍是[3333]构象，而羰基则在2-C位 置上。在晶体中，它们的优势构象为α－角顺取代[3333]-2-酮构象，而在溶液中 则取α－角顺取代和α－边外取代[3333]-2-酮两种构象，且两种构象处于动力学 平衡之中，以α－边外取代[3333]-2-酮构象占优势。     

双烯类聚合物的热分析——Ⅲ.铁与其它催化体系聚1,2-丁二烯及其衍生物的热分析

<正> 由不同催化体系制得的聚1,2-丁二烯,由于其立体规整性(如等规、间规和无规)不同,其形态、热学性质也会有所不同。关于它们的热学性质文献报道不多。我们曾报道,由三乙酰基丙酮钴-三异丁基铝-二硫化碳催化体系制备的间规聚1,2-丁二烯是晶态的;而由正丁基锂和MoCl_4OR-(i-Bu),AlOR′制得的是无规聚1,2-丁二烯;是非晶态     

~(13)C-NMR STUDY ON THE CHAIN TERMINAL STRUCTURE OF POLY-1,3-PENTADIENE POLYMERIZED WITH RARE EARTH CATALYST

The sequence distribution and the terminal structures of poly-1,3-pentadiene chains obtained by rare earth catalyst and effect of polymerization temperature on microstructure of the polymer have been investigated by ~(13)C-NMR method. According to experimental results it was supposed that terminal active growing chain of the polymer would be four types of anti- and syn-η~3-allyl structures. When polymerization temperature was reduced, the content of cis-1,4-poly-1,3-pcntadiene increases. It can be explained by isomerization between anti- and syn-η~3-allyl. The process forming trans-1,2 unit instead of 3,4-unit were also described.     

溶剂在丁腈基聚氨酯中的溶解和扩散

用石英弹簧法和示差扫描量热法 (DSC)、红外分光光度计 (FTIR)研究了苯、乙醇、丙酮、醋酸乙酯和1,2 二氯乙烷五种溶剂在端羟基聚丁二烯 丙烯腈共聚物为软段的聚氨酯中的溶解和扩散行为 .结果表明所有溶剂在丁腈聚氨酯中的扩散均为非费克扩散 ,且随着溶剂蒸汽压增大偏离费克扩散的程度增大 .相同相对蒸汽压下 1,2 二氯乙烷和醋酸乙酯偏离费克 (Fickian)扩散的程度较大 ,而乙醇、丙酮和苯则较小 ,这主要与它们和丁腈软段溶解度参数的极性分量和氢键分量有关 .1,2 二氯乙烷和苯在HTBN PU中的溶解度较高 ,而乙醇 ,醋酸乙酯和丙酮较低 ,主要与它们和丁腈软段溶解度参数的色散分量有关 .所有溶剂均表现出近似Flory Huggins型等温吸收曲线 .红外表明吸收溶剂后 ,氨基甲酸酯基团的氢键化程度有不同程度的下降 ,和溶剂与之形成氢键的能力大小有关 .力学性能表明非极性溶剂苯对材料的力学性能影响较小 ,而乙醇 ,醋酸乙酯和丙酮由于可与氨酯基团形成氢键 ,对原HTBN PU中氨酯键氢键的破坏大 ,力学性能下降大     

Synthesis of Optically Active β-Alkyl-α-methylene-γ-butyro- lactones from Enantioselective Biotransformation of Nitriles, an Unusual Inversion of Enantioselectivity

ＩｎｔｒｏｄｕｃｔｉｏｎＢｉｏｔｒａｎｓｆｏｒｍａｔｉｏｎｓｏｆｎｉｔｒｉｌｅｓ ,ｅｉｔｈｅｒｔｈｒｏｕｇｈａｎｉｔｒｉ ｌａｓｅ ｃａｔａｌｙｚｅｄｄｉｒｅｃｔｃｏｎｖｅｒｓｉｏｎｔｏｔｈｅｃａｒｂｏｘｙｌｉｃａｃｉｄｓｏｒｖｉａａｎｉｔｒｉｌｅｈｙｄｒａｔａｓｅ ｃａｔａｌｙｚｅｄｈｙｄｒａｔｉｏｎｔｏｔｈｅａｍｉｄｅｓｆｏｌｌｏｗｅｄｂｙｔｈｅｈｙｄｒｏｌｙｓｉｓｔｏｔｈｅａｃｉｄｓｍｅｄｉａｔｅｄｂｙａｎａｍｉｄａｓｅ ,ｈａｖｅｐｒｏｖｉｄｅｄａｕｓｅｆｕｌａｎｄｅｎｖｉｒｏｎｍｅｎｔａｌ…     

表面起伏光栅形成速率的影响规律 Ⅰ.偶氮生色团种类和官能度的影响

设计并合成了含有不同生色团以及不同官能度的环氧树脂基偶氮高分子 ,系统研究了偶氮生色团的种类和官能度对光栅形成速率的影响规律 .实验结果表明 ,偶氮苯对位是羧基的聚合物的光栅形成速率明显快于偶氮苯对位是硝基的聚合物 ,光栅形成速率随偶氮生色团官能度的增加而加快 .这两类聚合物都可以形成规整的可擦式表面起伏光栅     

硝酸酯分子几何构型的量子化学研究

运用MINDO / 3、MNDO 和AM1 三种半经验分子轨道(MO)方法, 通过SCF计算, 首次系统地获得了32个硝酸酯化合物分子的全优化几何构型。三种方法的计算结果与已报道的四个化合物(硝酸甲酯、吉纳、硝化甘油和太安)的实验结果相比, AM1法较好。所有硝酸酯的酯基(-ONO~2)具有近似不变的几何参数。直链烷基硝酸酯的键长和键角极为相近, 全部重原子均共平面。二元直链和四元硝酸酯具有对称的分子构型。     

Assembly of azido- or cyano-bridged binuclear complexes containing the bulky [Mn(phen)2]2+ building block: syntheses, crystal structures, and magnetic properties

Two new cyano-bridged heterobinuclear complexes, [Mn(II)(phen)2Cl][Fe(III)(bpb)(CN)2] x 0.5CH3CH2OH x 1.5H2O (1) and [Mn(II)(phen)2Cl][Cr(III)(bpb)(CN)2] x 2H2O (2) [phen = 1,10-phenanthroline; bpb(2-) = 1,2-bis(pyridine-2-carboxamido)benzenate], and four novel azido-bridged Mn(II) dimeric complexes, [Mn2(phen)4(mu(1,1)-N3)2][M(III)(bpb)(CN)2]2 x H2O [M = Fe (3), Cr (4), Co (5)] and [Mn2(phen)4(mu(1,3)-N3)(N3)2]BPh4 x 0.5H2O (6), have been synthesized and characterized by single-crystal X-ray diffraction analysis and magnetic studies. Complexes 1 and 2 comprise [Mn(phen)2Cl]+ and [M(bpb)(CN)2]- units connected by one cyano ligand of [M(bpb)(CN)2]-. Complexes 3-5 are doubly end-on (EO) azido-bridged Mn(II) binuclear complexes with two [M(bpb)(CN)2]- molecules acting as charge-compensating anions. However, the Mn(II) ions in complex 6 are linked by a single end-to-end (EE) azido bridging ligand with one large free BPh4(-) group as the charge-balancing anion. The magnetic coupling between Mn(II) and Fe(III) or Cr(III) in complexes 1 and 2 was found to be antiferromagnetic with J(MnFe) = -2.68(3) cm(-1) and J(MnCr) = -4.55(1) cm(-1) on the basis of the Hamiltonian H = -JS(Mn)S(M) (M = Fe or Cr). The magnetic interactions between two Mn(II) ions in 3-5 are ferromagnetic in nature with the magnetic coupling constants of 1.15(3), 1.05(2), and 1.27(2) cm(-1) (H = -JS(Mn1)S(Mn2)), respectively. The single EE azido-bridged dimeric complex 6 manifests antiferromagnetic interaction with J = -2.29(4) cm(-1) (H = -JS(Mn1)S(Mn2)). Magneto-structural correlationship on the EO azido-bridged Mn(II) dimers has been investigated.