Conformational state of benzilidene aniline derivatives from ab initio calculation and NMR spectroscopy data

Quantum chemical calculations of the structure and conformational state of a number of Shiff bases have been performed. ¹³C NMR spectra of investigated molecules were calculated and compared with experimental data to test verification of the used calculation model. The effect of terminal substituents on the conformation of azomethines and a relation between the conformation and ¹³C NMR chemical shift were examined.     

锰/钴-二氰胺-4-(1-咪唑基)苯胺三元配合物的合成与结构表征

以二氰胺钠[Na(dca)]和4-(1-咪唑基)苯胺(L)为共配体分别与锰盐和钴盐反应合成了2种新的配合物：零维[Mn(L)₂(dca)₂(H₂O)₂] (1)和二维[Co(L)₂(dca)](dca)_0.5(ClO₄)_0.5·1.5H₂O·MeOH (2)。通过元素分析、红外光谱和X射线单晶衍射对其进行了表征。配合物1属于三斜晶系，P1空间群。配合物2晶体属于正交晶系，Cmcm空间群。配合物1是1个中心对称的单核结构，锰(Ⅱ)离子与分别来自2个dca和2个L配体的4个氮原子以及2个水分子配位，形成八面体配位几何，L和dca均为单齿配位；配合物2是由混合桥dca和L组装成的二维配位聚合物网状结构，相邻的二维网以面对面方式堆积，沿c轴方向形成一维孔道，里面填充着未配位的反离子和溶剂分子。     

Crystal structure and luminescence of antimony(III) chloride complex with anilinium chloride

Crystal structure of (C₆H₅NH₃)₃[SbCl₅]Cl·H₂O is determined by X-ray analysis (a = 9.4155(13) Å, b = 11.4344(16) Å, c = 13.1584(18) Å, α = 113.483(2)°, β = 90.383(2)°, γ = 97.323(2)°, space group P \(\bar 1\), Z = 2, ρ_calc = 1.642 g/cm³). The crystal structure is based on [SbCl₅]^2? anions, anilinium cations (C₆H₅NH₃)⁺, isolated Cl^? anions, and water molecules. Structural features responsible for spectral and luminescent properties of the complex are discussed.     

The chemical oxidative polymerization of aniline in water: Raman spectroscopy

The structural changes of aniline oligomers and polyaniline, associated with oxidation of aniline with ammonium peroxydisulfate in aqueous solutions without any added acid, were studied. The reaction was quenched at various times and the films deposited on silicon windows have been studied in detail by Raman spectroscopy, at excitation wavelengths 633 and 514 nm. The presence of substituted phenazine structural units, in addition to ordinary benzenoid, quinonoid, and semiquinonoid structures, has been proved by the appearance of characteristic Raman bands at 1645–1630, 1420–1400, 1380–1365, ∼575, and ∼415 cm⁻¹. The remarkable differences of the Raman spectra of oligoanilines, precipitated in the first phase of oxidative polymerization, and polyaniline nanotubes and nanorods, formed in the second stage of reaction, are discussed. Copyright © 2008 John Wiley & Sons, Ltd.     

蒙脱土负载碘催化多组分合成咪唑衍生物

以苯偶酰(1)、苯甲醛(2a)、苯胺(3)和醋酸铵（4)为原料,蒙脱土负载碘和三乙烯二胺（DABCO）为催化剂,通过多组分法合成了6种1,2,4,5-四芳基-1,3-咪唑衍生物,其结构经¹H NMR和IR确证。对反应条件进行了优化。结果表明：在最优反应条件｛以10 mol%MMT/I₂为催化剂,10 mol%DABCO为碱,正丁醇为溶剂,原料配比r［n(1）：n(2a) ：n(3) ：n(4)］=1.0：2.0：2.0：8.0,于110 ℃反应16 h｝下,产率最高为91.5%。     

固体酸催化二氟二苯甲酮和苯胺缩合合成N-(双(4-氟苯基)亚甲基)苯胺

以固体酸为催化剂,4,4’-二氟二苯甲酮与苯胺脱水缩合,合成了N-(双(4-氟苯基)亚甲基)苯胺.比较了不同固体酸催化剂H型ZSM-5、Na型ZSM-5、介孔分子筛MCM-41(Al)及强酸型离子交换树脂Amberlyst 15的催化效果.使用比表面、NH3-TPD对催化剂进行了表征,并与催化效果关联.考察了催化剂用量、原料摩尔比、浓度及溶剂等反应条件对产物收率的影响.产物通过熔点、核磁共振谱进行了表征.结果表明,HZSM-5固体酸催化剂具有优异的催化作用.在优化条件下,以对二甲苯为反应溶剂和脱水剂,4,4’-二氟二苯甲酮0.1 mol,苯胺0.2 mol,催化剂用量2.0 g,反应24 h,产物收率达91%.此外,催化剂易于分离,能够重复使用多次.     

萘基薁并[2,1-d]嘧啶-4-胺类衍生物的合成

研究了萘基薁并[2,1-d]嘧啶-4-胺类衍生物的合成方法.以托酚酮、萘乙酸乙酯、N,N-二甲基甲酰胺二甲缩醛(DMF-DMA)及芳香胺为原料,依次经过氯代、缩合、环加成、环化反应得到目标产物.该反应操作简单、条件温和、收率良好.产物的结构经1H NMR,IR及元素分析等得以证实.     

碱土金属氧化物对丙三醇和苯胺气相合成3-甲基吲哚的Cu/SiO2-Al2O3催化剂的作用（英文）

研究了碱土金属氧化物的添加对丙三醇和苯胺气相合成3-甲基吲哚的Cu/SiO2-Al2O3催化剂性能的影响,采用X射线衍射、透射电镜、H2程序升温还原、NH3程序升温脱附以及热重-差热等技术对催化剂进行了表征.结果表明,MgO能加强活性组分和载体之间的相互作用,从而促进铜粒子在载体上的分散.另外,MgO能增加弱酸中心数,并且抑制积炭的形成,因而Cu-MgO/SiO2-Al2O3催化剂性能大大提高;而CaO,SrO或BaO的加入不利于Cu/SiO2-Al2O3催化剂上3-甲基吲哚的生成.这是由于铜粒子在载体上的分散度变差,而且在Cu-SrO/SiO2-Al2O3及Cu-BaO/SiO2-Al2O3催化剂上弱酸中心数较少.碱土金属氧化物的加入不能改变催化剂上积炭的结构.     

组合型Pt3Sn/Al2O3催化剂用于芳香硝基化合物一锅法合成N-烷基芳胺

采用吸附法制备了组合型Pt₃Sn/Al₂O₃双金属催化剂, 将该催化剂用于芳香硝基化合物原位液相加氢一锅法合成N-烷基芳胺. 研究表明, 在503 K, 空速为7.5 h^-1, 水体积分数为5%时, 1%(质量分数)Pt₃Sn/Al₂O₃催化剂具有较高的催化性能, 硝基苯的转化率为100%, N-乙基苯胺和N,N-二乙基苯胺的总选择性为98.2%. 同时,该催化剂对原位液相加氢烷基化反应具有一定普适性, 本文研究的14 种芳香硝基化合物与低级脂肪醇反应,均具有较高的N-烷基化产率.     

Gelation of a liquid electrolyte with aniline for use in a quasi-solid-state dye-sensitized solar cell

A new kind of gel electrolyte containing only organic solvents and an iodide salt-namely 3-methoxypropionitrile(MPN),aniline and AlI 3 -has been prepared.Gel formation results from the Lewis acid-base interaction between the Lewis acid ionic conductor AlI 3 and the Lewis base organic solvent aniline and no additional gelling agent is required.The AlI 3-aniline complex acts both as an ionic conductor and as a gelling agent.The differences between the peaks characteristic of the-NH 2 group and aromatic ring in the FTIR spectra of free aniline and the AlI 3-aniline hybrid confirm the formation of the AlI 3-aniline complex.The photovoltaic performance and long-term stability of dye-sensitized solar cells can be greatly enhanced by the addition of aniline to the AlI 3-MPN liquid electrolyte.