A Novel Method for Synthesizing 4,4′-Bis(hydroxymethyl)-2,2′-bipyridine

IntroductionSince C. W. Tang firstly reported theelectroluminescence of 8- hydroxyquinolinealuminium[1] ,much attention has been paid to themetal complexes as electro- luminescent materials.Based on a series of experimental data,it has beenknown that the electroluminescence of metalcomplexes with heterocyclic ligands containing Nand O elements mainly results from the tripletstatetransition.For some transitional metal complexes,there exist the transitions from metal to ligand( MLCT) at thei…     

六氟磷酸二(2,2′-联吡啶)(2,2′-联吡啶-4,4′-二羧酸)合钌(Ⅱ)的二维核磁共振谱分析

利用核磁共振氢谱和碳谱研究了电化学探针六氟磷酸二(2,2′-联吡啶)(2,2′-联吡啶-4,4'-二羧酸)合钌(Ⅱ)的立体结构,并通过二维1H-1H同核相关及1H-13C异核相关技术对其氢谱和碳谱进行了归属.     

Preparation and Spectroscopic Properties of Tris(2,2′-bipyridine)ruthenium(Ⅱ) Loaded in Siliceous Mesoporous MCM-41

[Ru(bpy)3]2+/MCM-41 composite material obtained by loading tris(2,2′-bipyridine)ruthenium(Ⅱ)([Ru(bpy)3]2+) in siliceous mesoporous MCM-41 was characterized by X-ray powder diffraction, UV-Vis absorption and emission spectroscopies. The absorption spectrum of [Ru(bpy)3]2+/MCM-41 is similar to that of [Ru(bpy)3]2+ aqueous solution, whereas its emission spectrum exhibits hypsochromic shift compared to the solution spectrum. On the other hand, the peak position of the emission spectrum of [Ru(bpy)3]2+/MCM-41 shifts towards longer wavelength when the loading amount increases.     

Hydrothermal Synthesis and Crystal Structure of a Manganese(II) Coordination Polymer with 1,1′-Biphenyl-2,2′,6,6′-tetracarboxyl Acid and 2,2′:6,2′′-Terpyridine Ligands

The title compound {[Mn(H2BPTC)(tpy)(H2O)]·(H2O)3}n (1, H4BPTC = 1,1′- biphenyl-2,2′,6,6′-tetracarboxylic acid, tby = 2,2′:6,2′′-terpyridine) has been synthesized by the hydrothermal reaction, and its structure was determined by X-ray diffraction and characterized by elemental analysis, IR spectrum and thermogravimetric analysis. The crystal is of monoclinic, space group P21/c with a = 10.971(2), b = 20.776(4), c = 14.332(3) , β = 109.25(3)o, MnC31H27N3O12, Mr = 688.50, V = 3084.1(10) 3, Dc = 1.483 g/cm3, F(000) = 1420, μ = 0.498 mm-1, S = 1.066 and Z = 4. The final refinement gave R = 0.0447 and wR = 0.1103 for 5107 observed reflections with I > 2σ(I). The title complex has a {[Mn(H2BPTC)(tpy)(H2O)]}n chain structure, and the hydrogen bonding interactions make it more stable. Each chain is further connected to the adjacent ones through π···π, C-H···π and rich hydrogen bonds to form a metal-organic coordination polymer.     

Microwave promoted one-pot synthesis of 3-(2′-amino-3′-cyano-4′-arylpyrid-6′-yl)coumarins

A facile procedure for the synthesis of 3-(2′-amino-3′-cyano-4′-arylpyrid-6′-yl)coumarins are being reported starting from 3- acetylcoumarin,aromatic aldehydes and malononitrile.The reactions were carded out on microwave irradiation in good yield with short time and easy work-up.The structures of all the compounds have been confirmed on the basis of their analytical,IR,~1H NMR, and mass spectral data.     

2,4,6-三(2′-吡啶基)-1,3,5-三嗪分光光度法测定Fe(Ⅱ)和Fe(Ⅲ)的研究

研究了F-掩蔽Fe(Ⅲ ) ,2 ,4,6 三 (2′ 吡啶基 ) 1 ,3 ,5 三嗪 (TPTZ)作显色剂测定Fe(Ⅱ )和Fe(Ⅲ )的适宜条件。实验结果显示 :在 0～ 2 .0 μg mLFe(Ⅱ )范围内符合比耳定律 ,RSD≤ 2 .4% ,回收率范围 95 .6 %～ 1 0 3 .5 % ,吸光度至少稳定 1 2h ,ε593 =2 .2 7×1 0 4L·mol-1 ·cm-1 ,灵敏度是邻菲口罗啉法的 2倍。适用于同时测定水中Fe(Ⅱ )和Fe(Ⅲ )。     

Co(μ2-bpy)V2O6(bpy=4,4′-联吡啶)的水热合成和晶体结构

采用CoCl2·6H2O、4,4′-联吡啶和NH4VO3,以H2O作溶剂(摩尔比1:2:2:1950)在170℃下水热反应合成无机-有机杂化化合物Co(μ2-bpy)V2O6(bpy=4,4′-联吡啶),经单晶X射线衍射测定其晶体结构.此晶体属三斜晶系,空间群为Pi,晶胞常数a=0.81599(7)nm,b=0.85826(7)nm,c=1.02031(8)nm,α=87.111(2)°,β=75.305(2)°,y=74.784(2)°,Z=2.Co(μ2-bpy)V2O6是无机的双金属氧化物层,[Co2V4O12]n通过有机的桥式配体μ2-bpy以N-Co配位键桥联而成.晶体的三维共价结构含有多种开放式孔道,其中最大孔道的尺寸为0.5nm×0.7nm.漫反射光谱研究表明,此晶体具有约2.0 eV的光学能隙,属于半导体,在420℃以下是热稳定的.     

Co(μ2-bpy)V2O6 (bpy =4,4′-联吡啶)的水热合成和晶体结构

采用CoCl2•6H2O、4,4′-联吡啶和NH4VO3,以H2O作溶剂（摩尔比1∶2∶2∶1950）在170 ℃下水热反应合成无机-有机杂化化合物Co(μ2-bpy)V2O6 (bpy=4,4′-联吡啶), 经单晶X射线衍射测定其晶体结构.此晶体属三斜晶系,空间群为Pī,晶胞常数a=0.81599(7) nm,b=0.85826(7) nm, c=1.02031(8) nm,α=87.111(2)°, β=75.305(2)°,γ=74.784(2)°, Z=2. Co(μ2-bpy)V2O6是无机的双金属氧化物层,[Co2V4O12]n通过有机的桥式配体μ2-bpy以N－Co配位键桥联而成.晶体的三维共价结构含有多种开放式孔道,其中最大孔道的尺寸为0.5 nm×0.7 nm.漫反射光谱研究表明,此晶体具有约2.0 eV的光学能隙,属于半导体,在420 ℃以下是热稳定的.     

铜(II)酪氨酸乙酯络合物催化一锅法合成S(-)-1,1-′联萘-2,2′-二酚

利用“一锅法” ,以L 酪氨酸乙酯为原料和铜 (II)反应生成络合物 ,不对称催化氧化偶合 2 萘酚合成S ( -) 1,1′ 联萘 2 ,2′ 二酚 ,选择最佳反应条件 ,可使化学产率达到 67%,光学产率达到 62 %.     

Effect of Co-solvent and Pressure on the Thermal Decomposition of 2,2′Azobis-(isobutyronitrile) in Supercritical CO_2

Recently, researchers pay much attention to the polymerization in supercritical (SC) CO2. 2, 2(-Azobis (isobutyronitrile) (AIBN) is a commonly used initiator in free radical polymerization in supercritical CO21. It is well known that the decomposition rate of the initiator AIBN plays an important role for a polymerization process2. Guan et al. have studied the effect of pressure on the decomposition rate of AIBN in SC CO22. A small amount of polar cosolvent can influence the propertie…     

Theoretical study on the hydrolysis mechanism of N,N-dimethyl-N′-(2′,3′-dideoxy-3′-thiacytidine)formamidine

The hydrolysis mechanisms of N,N-dimethyl-N′-(2′,3′-dideoxy-3′-thiacytidine)formamidine (FA-3TC) in the gas phase and in aqueous solution were studied by use of the density functional theory B3LYP/6-31 G(d, p) method. Two possible reaction pathways in the title reaction were considered. In one pathway water attacks the C=N double bond first (path A) while in the other water attacks the C—N single bond first (path B). The calculated results indicate that the first step in both pathways is the rate-limiting process and path A is more favorable than path B in the gas phase. The effect of solvent water on the title reaction was assessed at the B3LYP/6-31 G(d, p) level of theory based on the po-larizable continuum model (CPCM). In water the first mechanism (path A) is also favored.     

STUDY ON THE CHAIN-EXTENDING REACTION OF POLY (ETHYLENE TEREPHTHALATE) WITH 2, 2′-BIS (4H-3, 1-BENZOXAZIN-4-ONE)

2,2'-Bis (4H-3, 1-benzoxazin-4-one) (BBON) has been proved to be an effective chainextender for poly (ethylene terephthalate) (PET). In order to study the reaction mechanismand kinetics of chain-extending reaction, β-bishydroxyethylene terephthalate (BHET) wasselected as model compound. The NMR data, IR spectra and number average molecularweight (M_n) of the products obtained from the reaction of BBON and BHET verify thatBBON is a hydroxyl-reactive extender. The mechanism was discussed. Kinetics dataindicate that extending reaction is a second order reaction, and BBON has high reactivity.The activation energy (E_a) was measured.     

新颖的镧-2-氟苯甲酸及2,2′-联吡啶配合物的合成与晶体结构(英文)

2-fluorobenzoic acid (2-HFBA) and 2,2′-bipyridine (2,2′-bpy) was used as ligands to react with lanthanum to obtain a complex, [La(2-FBA)3·(2,2′-bpy)]2. The structure of the complex contains three independent molecules. In two of them, the two central metal ions are connected together through four 2-FBA groups by bidentate bridging and chelating-bridging two modes. In another, the two central metal ions are connected together through four bidentate bridging 2-FBA groups.     

叠氮二(2,2′-联吡啶)钌(Ⅱ)配合物的光物理和光化学性质

本文研究了叠氮二(2,2′—联吡啶)钌(Ⅱ)配合物在有机溶剂及乙腈—水中的一些光物理和光化学性质。在77K的甲醇—乙醇玻璃态时,用245nm等波长激发表现较强的荧光,其最大发射峰在540nm,另一弱带在580nm。在室温甲醇中测得的磷光发射是弱的,且寿命<15us。 在254nm、300nm及514nm照射下,光反应机制及量子产率与溶剂、照射波长有关。在乙腈—水及乙腈中,分别用254nm和514nm照射均发生取代反应,最后的光产物为Ru(bpy)_2(N_3)(CH_3CN)~ ,配合物消失的量子产率分别为0.129±0.008mol einstein~(-1)及(6.77±0.22)×10~(-5)mol einstein~(-1);在乙腈—水中用514nm照射,生成的光产物先是Ru(bpy)_2(N_3)(CH_3CN)~ ,再生成Ru(bpy)_2(CH_3CN)_2~(2 ),配合物消失的量子产率为(5.32±0.13)×10~(-4)mol einstein~(-1)。     

Resolution and Crystal Structure of 9α-(3-Azabicyclo[3,3,1]nonanyl)- 2′-cyclopentyl-2′-hydroxyl-2′-thienylacetate

1 INTRODUCTION The design, development and marketing of new chiral drugs are now a major theme in the drug chirality research and industry[1]. In 1996, the FDA announced it would consider further incentives for developing single isomer drugs because of their bet- ter pharmacokinetics prosperity, safety, and tolera- bility. Our recent drug candidate, 9α-(3-azabicyclo- [3,3,1]nonanyl)-2?-cyclopentyl-2?-hydroxyl-2?-thien- ylacetate I, is a potential selective M1 antagonist. It is composed…     

(R)-1，1′-联萘手性单元通过溶胶凝胶法合成杂化硅干凝胶(英)

Precursor molecule (R)-6,6′-bis(triethoxysilylethen-2-yl)-2,2′-di(methoxyethoxymethyloxy)-1,1′-binaphthyl (R-2) was synthesized by Pd-catalyzed Heck reaction of (R)-6,6′-dibromo-2,2′-di(methoxyethoxymethyloxy)-1,1′-binaphthyl (R-1) intermediate with vinyltriethoxysilane. The hydrolysis and polycondensation of the precursor R-2 produced the corresponding xerogel. Both precursor and xerogel were analysed by NMR, FTIR, UV, CD spectra, fluorescent spectroscopy, polarimetry and elemental analysis. The precursor and xerogel can emit strong blue fluorescence and are expected to have a potential application in the separation of chiral molecules as fluorescent sensor. The precursor exhibits strong Cotton effect in its circular dichroism (CD) spectrum indicating a highly rigid structure.     

Copper(Ⅱ) and 2,2′-Biimidazolyl-promoted Ullmann Coupling Reaction of Phenols and Aryl Iodides

Ullmann-type diaryl ether synthesis can be performed at 100℃ in good to excellent yields by aryl iodides asthe substrates under the assistance of copper(Ⅱ)and 2,2'-biimidazolyl.     

铜(Ⅱ)与反式丁烯二酸根和2,2′-联吡啶配合物的研究

合成了铜(Ⅱ)与反式丁烯二酸根和2,2＇-联吡啶形成的配合物,并进行了元素分析、红外光谱、电子反射光谱和变温磁化率等研究,确定其组成为[Cu_2(fum)(bipy)_4][fum]·12H_2O,其中bipy=2,2＇-联吡啶,fum=反式丁烯二酸根.测定了配合物的晶体结构,[Cu_2(fum)(bipy)_4][fum]·12H_2O晶体属三斜晶系,P1(＃2)群;晶胞参数:α=1.0697(2)nm,b=1.2820(2)nm,c=1.0470(3)nm,α=101.88(2)°,β=101.93(2)°,γ=79.41(1)°;Z=1,最终偏离因子R=0.033.分子为反式丁烯二酸根桥联两个Cu(Ⅱ)单元的双核结构,每个Cu(Ⅱ)具有畸变的三角双锥配位环境.变温磁化率研究表明,配合物中存在弱的铁磁性偶合作用.     

2′-(2-噻吩亚甲基)-2-羟基苯甲酰腙钴(Ⅲ)配合物的合成、表征及晶体结构

In ethanol, a mononuclear cobalt(Ⅱ) complex incorporating 2′-(2-Thienylidene)-2-Hydroxybenzoylhydra-zide has been synthesized and characterized by IR, UV-Vis, elemental analysis and X-ray crystal structure analysis. The crystal belongs to triclinic system, space group P1 with cell constant, a=1.230 69(10) nm, b=1.329 18(11) nm, c=1.330 56(11) nm, α=113.702(2)°, β=91.590(2)°, γ=100.846(2)°, V=1.944 4(3) nm³, Z=2, μ=0.662 mm^-1, D_c=1.482 g·cm^-3, F(000)=896, R_int=0.048 7. The crystal structure shows an anionic didentate ligand O and N donors in this work. The cobalt(Ⅲ) atom is hexacoordinated with oxygen atom from keto group and nitrogen atom from amide to form a cobalt atom for the core octahedral structure. CCDC: 748882.     

四氯化和四硝酸合双(4,4′-二甲基-2,2′-联吡啶)铈(Ⅳ)配合物的研究

在关于有机碱的(RH)_2CeCl_6型配合物的研究中,有许多报道称有机碱在配合物中不参与配位,只起中和酸的作用,然而Ce~(4+)的配位数通常高于,因此在(RH)_2CeCl_6型配合物中,Ce~(4+)与某些有机碱中的N原子配位以满足其较高配位数也是可能的,我们合成了4,＇二甲基 2,2＇-联吡啶铈(Ⅳ)氯化二物和硝,酸盐两个新配合物,通过实验研究发现这两种配合物性质相似,在4,4＇-二三甲基-2,2＇-联吡啶铈(Ⅳ)硝酸盐