Synthesis and biological evaluation of novel phane-structured diazacrowns containing γ-piperidone and pyridine rings

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Synthesis,coordination and extraction properties of 2,3-bis(diphenylphosphoryl)pyridine toward f-block elements

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Synthesis,X-ray crystallographic studies,DFT calculations and nanostructural features of annulated imidazo[4,5-b]pyridine derivatives

Friedländer-type condensation of 5-amino-4-cyano-1-(phenyl/p-substitutedphenyl)imidazole with cycloalkanone was done by refluxing the mixture with a suspension of anhydrous aluminum chloride in dry 1,2-dichloroethane to produce 7-amino-3-aryl(5,6)cycloalkanoimidazolo[4,5-b]pyridine. Single X-ray crystallographic diffraction studies had shown that compounds had different types of heterodimeric, homodimeric π–π stacking, T-type stacking, and intermolecular hydrogen bonds which lead to nanostructure formation detected by scanning electron microscope. DFT calculation had also been performed to quantify heterodimeric π–π and T-stacking interactions.     

Optical properties of a novel fluorene‐based thermally stable conjugated polymer containing pyridine and unsymmetric carbazole groups

A new diiodo monomer containing heterocyclic pyridine and carbazole groups was synthesized via Chichibabin reaction and used in the preparation of a conjugated polymer via Suzuki coupling approach. The conjugated polymer was highly soluble in common organic solvents such as NMP, THF, dichloromethane, chloroform, toluene, xylene, and benzene at room temperature. The polymer had high glass transition temperature at 191 °C and T_d10 at 434 °C in nitrogen atmosphere. The pristine polymer exhibited the UV–vis maximum absorption at 355 nm and shifted to 420 nm after protonation. The emission of the polymer in THF solution changed from the blue region with maximum peak at 400 nm to the yellow region with maximum peak at 540 nm after protonated by HCl, and the intensity of emission depended on the concentration of acid. The polymer also showed electrochromic behavior under applied voltage. The emission color of the polymer film changed from blue (435 nm) to yellow (570 nm) when 2.5 V bias voltage was applied. The polymer also exhibited write‐once and read‐many‐times (WORM) polymer memory effect with tristable states. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 991–1002, 2009     

Theoretical studies on high energetic density nitramine explosives containing pyridine

The insensitive property of explosives containing pyridine is combined with the high energy of nitramine explosives,and the concept of new nitramine explosives containing pyridine is proposed,into which nitramine group with N N bonds is introduced as much as possible.Based on molecular structures of nitramine compounds containing pyridine,density functional theory(DFT) calculation method was applied to study designed molecules at B3LYP/6-31+G(d) level.The geometric and electronic structures,density,heats of formation(HOF),detonation performance and bond dissociation energies(BDE) were investigated and comparable to 1,3,5-trinitro-1,3,5-triazinane(RDX) and 1,3,5,7-tetranitro-1,3,5,7-tetrazocane(HMX).The simulation results reveal that molecules B and D perform similarly to traditionally used RDX.Molecule E outperform RDX,with performance that approach that of HMX and may be considered as potential candidate of high energy density compound(HEDC).These results provide basic information for molecular design of novel high energetic density compounds.     

溴化苄基取代吡啶类季铵盐的制备和抗菌性能

抗菌材料和抗菌制品的研究与应用一直是世界各国研究的重要课题~([1-3]),其中有机抗菌剂占据主要地位.季铵盐是研究比较多的一类有机抗菌剂,它们表现出良好的物理性质,如胶束浓度低,黏弹性好和溶解性强~([4]),同时此类抗菌剂具有强效的抗菌作用~([5]),引起了人们的极大兴趣.季铵盐广泛应用于医药、卫生、食品、饲料工业、农业、纺织、塑料、橡胶、造纸、水处理、油田开采、涂料、日常生活等多种领域~([6-10]).     

Blends of metal acetates and polyurethanes containing pyridine groups II. SAXS and EXAFS studies

Polyurethanes containing pendant pyridine units were blended with various metal acetates and studied by small-angle x-ray scattering (SAXS) and extended x-ray absorption fine structure spectroscopy (EXAFS) to better understand the microscopic effect of blending on these materials. An earlier investigation found a dramatic enhancement in mechanical properties after blending, which suggests at least two pyridine units were coordinating to a single cation. This coordination would enable the cation to act as a cross-linking site, which could then cause the observed changes in mechanical properties. To determine the effect of complexation on the microphase-separated domain structure, small-angle x-ray scattering patterns were collected. Neutralization with a metal acetate increased the scattered intensity, which can be explained by an increase in electron density contrast but may also have been due to an improvement in phase separation. The distance between lamellar domains was basically unaffected by the addition of metal acetate, with the exception of nickel acetate. In this instance the distance decreased, which was caused by an improvement of packing inside the hard segments. EXAFS at the nickel and zinc edges indicated that the same qualitative changes occurred in the local environments around both cations after blending versus the unblended acetates. The magnitude of the first shell peak in the radial structure function (RSF) increased significantly upon blending, a result that is difficult to rationalize. The higher shell peaks exhibited significant changes in position and magnitude upon blending, which indicates substantial local rearrangement around the metal cation These fundamental changes in the EXAFS spectra may have been due to complexation between the cation and the pyridine group, but the results were not conclusive. © 1994 John Wiley & Sons, Inc.     

含吡啶联喹啉羧酸新型配体的合成和表征

以4-乙酰基吡啶(2)、2,6-二乙酰基吡啶(3)为底物分别与靛红及取代靛红(1a-1g)在KOH做催化剂的条件下,以10%的乙醇溶液作为溶剂进行反应,以41.4%-90.5%的产率得到了结构新颖的含氮联喹啉酸有机配体(4a-4g)和(5a-5g),它们的结构均通过红外光谱、核磁共振氢谱、核磁共振碳谱和质谱得以证实。以上制备过程具有反应条件温和、后处理简单、环境友好等优点,为制备含吡啶联喹啉羧酸新型配体提供了简单有效的方法。     

New dioxadiaza-, trioxadiaza- and hexaaza-macrocycles containing dibenzofuran units

New dioxadiaza-, trioxadiaza-, and hexaaza-macrocycles containing rigid dibenzofuran groups (DBF) were prepared by a convenient synthetic route in high yields. The structures of the macrocycles were unequivocally established by electrospray mass spectrometry (ESIMS) studies together with NMR spectroscopy, with the exception of [14](DBF)N₃. The structures of the copper complex of [14](DBF)N₃ and of the diprotonated form of [22](DBF)N₂O₃ were determined by single crystal X-ray diffraction. Conformational analyses on the free macrocycles [14](DBF)N₃ and [22](DBF)N₂O₃ as well as on their larger counterparts containing two DBF units were undertaken in order to understand the synthetic findings.     

Synthesis, coordination studies and redox properties of a novel ditertiary phosphine bearing two ferrocenyl groups

The new ferrocenyl substituted ditertiary phosphine {FcCH₂N(CH₂PPh₂)CH₂}₂ [Fc = (η⁵-C₅H₄)Fe(η⁵-C₅H₅)] (1) was prepared, in 72% yield, by Mannich based condensation of the known bis secondary amine {FcCH₂N(H)CH₂}₂ with 2 equiv. of Ph₂PCH₂OH in CH₃OH. Phosphine 1 readily coordinates to various transition-metal centres including Mo⁰, Ru^II, Rh^I, Pd^II, Pt^II and Au^I to afford the heterometallic complexes {RuCl₂(p-cym)}₂(1) (2), (AuCl)₂(1) (3), cis-PtCl₂(1) (4), cis-PdCl₂(1) (5), cis-Mo(CO)₄(1) (6), trans,trans-{Pd(CH₃)Cl(1)}₂ (7) and trans,trans-{Rh(CO)Cl(1)}₂ (8). In complexes 2, 3, 7 and 8 ligand 1 displays a P,P′-bridging mode whilst for 4-6 a P,P′-chelating mode is observed. All new compounds have been fully characterised by spectroscopic and analytical methods. Furthermore the structures of 1, 2 · 2CH₂Cl₂, 3 · CH₂Cl₂, 4 · CH₂Cl₂, 6 · 0.5CHCl₃ and 8 have been elucidated by single crystal X-ray crystallography. Electrochemical measurements have been undertaken, and their redox chemistry discussed, on both noncomplexed ligand 1 and representative compounds containing this new ditertiary phosphine.     

Synthesis and smectogenic properties of novel phloroglucinol-based star-shaped liquid crystals containing three peripheral alkyloxylated Schiff base arms

A series of symmetrical trimeric liquid crystalline compounds of which the molecular structure with a central core of 1,3,5-benzene attached by three rod-like mesogenic Schiff base moieties via the propylene spacers and ether linkages has successfully been synthesised and characterised by infra red and nuclear magnetic resonance spectroscopic techniques. All the star-shaped compounds in this series exhibit predominantly SmC phase except the analogue possessing terminal C₈H₁₇ group. It is apparent that the members with even parity from C₁₀H₂₁ to C₁₆H₃₃ show enantiotropic SmC phase while the member with longest terminal chain of C₁₈H₃₇ is inclined to monotropic smectogen. The X-ray diffraction measurements reveal that the tilted smectic layer structures of the SmC phase are confirmed to have an obvious sharp peak at small angles of 2θ ～ 1.03°–1.48° with d-spacing values of 4.01–4.58 nm, which are corresponding to tilt angles of ～48° in the SmC phase.     

含酰胺键的吡啶双子表面活性剂合成及性能

以间苯二甲酰氯、氨基吡啶、氯乙酰氯和长链伯胺(n为8、12、14、16)为原料,通过酰胺化反应合成了1,3-二[N-(3-吡啶基)]苯甲酰胺(中间体A)和N-烷基-2-氯乙酰胺(中间体B)。中间体A和中间体B通过季铵化反应,合成目标产物(I₈,I₁₂,I₁₄,I₁₆)。利用¹H-NMR、FTIR对产物及中间体结构进行表征。通过电导率法测定了目标产物在25℃、35℃、45℃的临界胶束浓度(CMC),进行热力学参数计算。用吊环法测定了25℃时目标产物的表面张力γ,计算了相关的表面性能参数。测定目标产物在25℃下的稳泡性及乳化能力。结果表明,合成表面活性剂具有良好的表面活性、稳泡性和乳化能力。     

Synthesis and liquid crystalline properties of novel pyridine derivatives

The treatment of 4‐hydroxypyridine with cholestery p‐(ω‐bromoalkyloxy)benzoates in N,N‐dimethylformamide containing K₂CO₃ gave cholestery p‐[ω‐(4‐pyridyloxy)alkyloxy]benzoates, which exhibited liquid crystalline properties     

Synthesis, characterization, and DFT studies of a novel azo dye derived from racemic or optically active binaphthol

We present a new azo reactive dye from racemic or optically active BINOL. This dye was characterized by UV-vis, FTIR, mass, ¹H NMR, and ¹³C NMR spectroscopic techniques and elemental analysis. The structure and spectrometry of this azo dye have been investigated theoretically by performing HF and DFT levels of theory using the standard 6-31G^∗ basis set. The optimized geometries and calculated vibrational frequencies are evaluated via comparison with experimental values. The vibrational spectral data obtained from solid phase FTIR spectra are assigned based on the results of the theoretical calculations. The theoretical electronic absorption spectra have been calculated using CIS, TD-DFT, and ZINDO methods. In addition, a good agreement between calculated and experimental NMR data is observed.     

Synthesis and coordination properties of new bis(phosphinomethyl)pyridine N,P,P'-trioxides

In a search for more hydrocarbon solvent soluble derivatives of the parent ligand, 2,6-[Ph(2)P(O)CH(2)](2)C(5)H(3)NO (1a), a series of new ligands, 2,6-[R(2)P(O)CH(2)](2)C(5)H(3)NO [R = Bz (1b); Tol (1c); Et (1d); Pr (1e); Bu (1f); Pn (1g); Hx (1h); Hp (1i); and Oct (1j)] and 2,6-[RR'P(O)CH(2)](2)C(5)H(3)NO [R = Ph, R' = Bz (2a); R = Ph, R' = Me (2b); R = Ph, R' = Hx (2c); R = Ph, R' = Oct (2d)], have been prepared by either Arbusov or Grignard substitutions on 2,6-bis(chloromethyl)pyridine followed by N-oxidation. The new ligands have been characterized by spectroscopic methods, and their coordination chemistry with selected lanthanide ions has been surveyed. Several 1:1 and 2:1 ligand/metal complexes have been isolated, and single-crystal X-ray diffraction analyses for Nd(2a)(NO(3))(3), Er(2a)(NO(3))(3), Yb(1d)(NO(3))(3), and [Nd(1c)(2)](NO(3))(3) are described. The new structural data are discussed in relation to the structures of complexes formed by 1a.     

Synthesis of various camphor-based chiral pyridine derivatives

(+)-β-Hydroxymethylenecamphor 1 and enamines 2a-e were transformed into chiral camphor-based pyridine derivatives 3a-e via a tandem condensation reaction in good yields.     

新型偶氮苯金属液晶化合物的合成与性能研究

合成了新型偶氮苯金属配合物。 分别采用光谱分析、热分析及X射线衍射测试技术对样品进行了表征。结果表明,连接偶氮苯和金属配合物之间碳链的长度对该化合物的相转变和荧光特性具有特殊的影响。 该系列化合物在紫外光和热作用下具有99%以上的偶氮苯顺-反异构化反应效率;具有290和560 nm这2个波段荧光发射光谱。由其中一个金属液晶化合物分散在聚甲基丙烯酸甲酯网络而形成的介质可作为全息信息存储材料而实现全息图像的写入和读出。