1,10-邻菲啰啉并咪唑衍生物阴离子受体的合成及识别性能

设计合成了2个1,10-邻菲啰啉并咪唑衍生物阴离子受体2-(2-羟基苯基)-1H-咪唑[4,5-f][1,10]邻菲啰啉(1)和2-(2-羟基-5-溴苯基)-1H-咪唑[4,5-f][1,10]邻菲啰啉(2), 受体2的结构由X射线单晶衍射分析确证. 通过紫外-可见光谱滴定及 ¹H NMR滴定研究了这2个受体对F^-, Cl^-, Br^-, I^-, H₂PO₄^-和AcO^- 6种阴离子的识别传感作用及作用机理. 结果表明, 受体对AcO^-, F^-和H₂PO₄^-有较强的传感作用, 溶液颜色由淡黄色变为黄色; 对Cl^-的作用较弱; 而对Br^-和I^-则无明显作用. 通过机理研究发现, 受体与F^-, H₂PO₄^-和AcO^-形成1: 1的氢键超分子, 当阴离子的量超过受体的1倍以后, 咪唑氮上的氢转移到阴离子; 受体与Cl^-以氢键形成超分子复合物, 而与Br^-和I^-作用很弱.     

Off-on-off luminescent switching of a dye containing imidazo[4,5-f][1,10]phenanthroline

A new acid-base fluorescent switch containing both imidazo[4,5-f][1,10]-phenanthroline and triphenylamine groups has been synthesized.Its fluorescence emissions and absorptions can be reversibiy changed through protonation/deprotonation of imidazole and amine moiety by controlling the intramolecular charge transfer(ICT) process,leading to off-on-off fluorescent molecular switching.     

新型2-取代苯基-1H-咪唑[4,5-f][1,10]邻菲啰啉基Ru(II)配合物的光电性质

为获取具有活性官能团的接枝型、高性能荧光传感配合物,合成了2-(4-氨基苯基)-1H-咪唑[4,5-f][1,10]邻菲啰啉(CImPB-NH2)、2-(4-羟基苯基)-1H-咪唑[4,5-f][1,10]邻菲啰啉(CImPB-OH)、2-(4-羧基苯基)-1H-咪唑[4,5-f][1,10]邻菲啰啉(CImPB-COOH)和2-(4-硝基苯基)-1H-咪唑[4,5-f][1,10]邻菲啰啉(CImPB-NO2)四种配体,借助紫外-可见(UV-Vis)吸收光谱、荧光(PL)光谱、循环伏安法(CV)和含时密度泛函理论(TD-DFT)对上述四种配体与过渡金属元素钌(Ru)所形成的配合物的光电性能进行研究.结果表明:四种配合物均在可见光区域有较强吸收,发光范围覆盖绿色到红色光波段.在极性溶剂N,N-二甲基甲酰胺(DMF)中,以2-(4-氨基苯基)-1H-咪唑[4,5-f][1,10]邻菲啰啉为配体所构建的钌配合物([Ru(CImPB-NH2)(bpy)2]2+的荧光量子产率(Φ)较不含咪唑环的5-氨基邻菲啰啉合钌([Ru(phen-NH2)(bpy)2]2+)的提高了67%,以2-(4-羧基苯基)-1H-咪唑[4,5-f][1,10]邻菲啰啉所构建的钌配合物([Ru(CImPB-COOH)(bpy)2]2+)的Φ可达29.8%,是[Ru(phen-NH2)(bpy)2]2+的18倍.理论计算表明:配体中取代苯环、咪唑环和邻菲啰啉的稠环共平面,形成共价大π体系,其有效共轭长度较邻菲啰啉母体有显著增加,配合物是以Ru为中心的近似八面体构型,理论计算的电子吸收光谱和跃迁性质与实验结果相一致.上述研究有可能为接枝型、高性能荧光传感配合物的设计和筛选提供实验依据.     

微波辅助合成菲并咪唑衍生物及微波非热效应

以1,10-邻菲啰啉5,6-二酮及苯甲醛(或取代苯甲醛)为原料, 在微波辐射条件下制备了一系列菲并咪唑类衍生物, 考察了温度、 时间以及投料比对微波辅助合成菲并咪唑类衍生物的影响, 并进一步探讨了微波非热效应的影响. 设计正交实验优化了反应条件; 使用SiC管作为反应容器屏蔽微波对反应的影响; 通过元素分析、 核磁共振波谱、 质谱及红外光谱等对化合物进行了表征. 结果表明, 微波辅助反应的最佳反应条件为: 1,10-邻菲啰啉-5,6-二酮与苯甲醛(或取代苯甲醛)的投料比为1: 1.5, 反应温度为100℃, 反应时间为20 min; 并且发现SiC管中反应的产率明显低于石英管反应容器. 与传统制备方法相比, 微波辅助合成方法可在更短时间内快速方便地制得菲并咪唑类衍生物; 反应温度、 反应时间以及投料比对微波辅助合成反应有明显影响; 微波非热效应有助于提高反应产率.     

芳基咪唑并[4,5-f][1,10]菲咯啉的无溶剂绿色合成研究

以菲咯啉二酮、苯甲醛及其衍生物和醋酸铵为原料,采用无溶剂绿色研磨工艺,合成了芳基咪唑并菲咯啉化合物.通过对不同反应条件的筛选,得到一条高效、简便、绿色的合成芳基咪唑并菲咯啉化合物路线,不同的芳醛与菲咯啉二酮都可以较高的收率得到相应的芳基咪唑并[4,5-f][1,10]菲咯啉.     

An efficient synthesis of novel benzo[b]pyrido[3',2':4,5] thieno[2,3-e][1,6]naphthy-ridine-8-ones

An efficient method for the synthesis of novel benzo[b]pyrido[3',2':4,5] thieno[2,3-e][1,6] naphthyridine-8-one derivatives has been developed using a Pictet-Spengler reaction between 4-(3-aminothieno[2,3-b]pyridin-2-yl)quinoline-2-ones, which could be obtained from the alkylation of 4-bromomethylquinoline-2-ones with 3-cyanopyridine-2-thione followed by a Thorpe-Ziegler isomerization, and aromatic aldehydes under p-TsOH as catalysis in good yields.     

Crystal Structure of Adduct 2-Phenyl-imidazo [ 4,5-f ] 1,10-phenanthroline Methanol

The structure of the title adduct comprises a phenanthroline derivative 2-phenyl-imidazo[4,5-f]1,10-phenanthroline and a methanol.The composition of the crystalline adduct was characterized as C19H12N4.CH3OH.It belongs to orthorhombic system,space group Pna21 with a=1.3693(4)nm,b=2.2988(7)nm,c=0.51338(15)nm,V=1.6160(8)nm^3.Z=4,and final R1=0.0423.wR2=0.1012 .Crystal structure shows that all the 19 carbon atoms and 4 nitrogen atoms are coplanar.The bond length data indicated that a very extensive conjugation system was formed.This conjugation makes the compound being a potentially excellent energy transformer used for luminescent materials.     

Effective one-pot synthesis of tetrahydrobenzo[b]pyran derivatives using nickel Schiff-base complex immobilized on iron oxide nanoparticles

Nickel Schiff-base complex immobilized on silica-coated Fe₃O₄ as a heterogeneous catalyst was designed and characterized by different techniques, such as Fourier transform infrared (FT-IR), X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), inductively coupled plasma (ICP) and vibrating sample magnetometry (VSM) thermogravimetric analysis (TGA), and Brunauer–Emmett–Teller (BET). The synthesized nanocatalyst has been explored as a new and efficient recyclable heterogeneous catalyst for the one-pot three-component synthesis of tetrahydrobenzo[b]pyran derivatives. The reaction proceeds smoothly to supply the respective products in excellent yields and low reaction times. The catalyst can be easily recovered by a magnetic field and reused for eight consecutive reaction cycles without significant loss of activity.     

由N-苯基[1,3]苯并噁嗪正离子与烯烃[4+2]反应合成喹啉并[1,2-c][1,3]苯并噁嗪-6-酮衍生物

以BF3·OEt2 为催化剂, 在室温下通过4-羟基-N-苯基[1,3]苯并噁嗪-2-酮的脱羟基产生N-苯基[1,3]苯并噁嗪正离子, 然后与富电子烯烃发生Diels-Alder反应, 合成出了一系列喹啉并[1,2-c][1,3]苯并噁嗪-6-酮和喹啉并[1,2-c][1,3]萘并噁嗪-6-酮衍生物.     

p-Toluenesulfonic acid-catalyzed one-pot synthesis of 2-amino-4-substituted-1,4-dihydrobenzo[4,5]imidazolo[1,2-a]pyrimidine-3-carbonitriles under neat conditions

A simple, efficient, and green procedure for the preparation of 2-amino-4-substituted-1,4-dihydrobenzolo[4,5]imidazolo[1,2-a]pyrimidine-3-carbonitriles has been developed by multi-component condensation of 2-aminobenzimidazole with aldehydes and malononitrile in the presence of a catalytic amount of p-toluenesulfonic acid, affording excellent yields under neat conditions. The protocol avoids the use of expensive catalysts, toxic solvents, and chromatographic separation. We believe that this new environmentally metal-free procedure, combined to a solvent-free reaction, would be of importance in the search of green laboratory-scale synthesis.     

Fe3O4@MCM-48-SO3H:An efficient magnetically separable nanocatalyst for the synthesis of benzo[f]chromeno[2,3-d]pyrimidinones

Sulfonic acid groups were grafted onto three different types of synthesized magnetic nanoparticles, namely Fe3O4, Fe3O4@SiO2, and Fe3O4@MCM‐48. The sulfonic acid‐functionalized nanoparticles were evalu...     

Fe3O4@MCM-48–SO3H:合成苯并[f]色烯并[2,3-d]嘧啶酮的高效、可磁性分离纳米催化剂（英文）

Sulfonic acid groups were grafted onto three different types of synthesized magnetic nanoparticles, namely Fe3O4, Fe3O4@SiO2, and Fe3O4@MCM‐48. The sulfonic acid‐functionalized nanoparticles were evaluated as catalysts for the synthesis of 5‐aryl‐1H‐benzo[f]chromeno[2,3‐d]pyrimidine‐2,4(3H,5H)‐dione derivatives in terms of activity and recyclability. Their catalytic activities were compared with that of the homogeneous acid catalyst 1‐methylimidazolium hydrogen sulfate ([HMIm][HSO4]). The activity of Fe3O4@MCM‐48–SO3H was comparable to those of the other heter‐ogeneous and homogeneous catalysts.     

Ring-opening Copolymerization of Cyclohexene Oxide and Maleic Anhydride Catalyzed by Mononuclear [Zn（L）（H2O）] or Binuclear [Zn2（L）（OAc）2（H2O）] Complex Based on the Salen-type Schiff-base Ligand

From the self-assembly of the typical Salen-type Schiff-base ligand H2L and Zn(OAc)2·2H2O in the molar ratio of 1:1 or 1:2, the mononuclear [Zn(L)(H2O)](1) or binuclear [Zn2(L)(OAc)2(H2O)](2) are obtained, respectively. For both complexes 1 and 2, the unsaturated five-coordinate coordination environment to the catalytic active centers(Zn2+ ions) permits the monomer insertion for the effective solution copolymerization of cyclohexene oxide and maleic anhydride. All the solution copolymerizations afford poly(ester-co-ether)s, while lower catalyst and co-catalyst concentrations are helpful for the formation of alternating polyester. Of the three co-catalysts, 4-(dimethylamino)pyridine is found to be the most efficient, while an excess thereof is detrimental for chain growth of the copolymers.     

新型2-氧代-1,2,4-三唑并[3,2-d][1,5]苯并氧氮杂类稠杂环的合成

将取代色满酮 ( 1 )与芳肼反应生成的腙与 HNCO发生 [3 +2 ]环加成反应 ,加成产物 ( 2 )经氧化得到偕偶氮异氰酸酯 ( 3 ) .化合物 3在 HBF4 的催化下发生环化 -重排反应 ,得到新颖的三环系 2 -氧代 -1 ,2 ,4-三唑并[3 ,2 -d][1 ,5 ]苯并氧氮杂化合物 5 a～ 5 g     

An Efficient Synthesis of 2-Propyl-5-phenyl-1,4-dioxo-1,2,3,4,5,6,7, 8-octahydro-[1,4,2]diazaphosphorino[1,-2a][1,3,2] benzodiazaphosphorine 3-oxide

During the past two decades, a-ketophosphonates and their derivatives have attracted considerable attention because of their special physical, chemical and pharmacological properties due to the proximity of the carbonyl and the phosphoryl groups1-12. In the study on new pharmaceuticals and agrochemicals, the application of heterocycles is suggested to improve the biological activity. A sizeable number of endogenous fused heterocyclic compounds play a key role in regulation of various life pr…     

室温下Cu掺杂的ZnO纳米粉末催化多组分一锅法合成完全取代的茚并[1,2-b]吡啶(英文)

Cu doped ZnO nanocrystalline powder(10 mol%) has been found to be an efficient catalyst for the one‐pot multi‐component synthesis of fully substituted new indeno[1,2‐b]pyridines through a com-bination of 1,3‐indandione, propiophenone or acetophenone derivatives, aromatic aldehydes, and ammonium acetate in ethanol/H2 O at room temperature. The methodology is mild, efficient and high to excellent yielding.     

新型镉配合物[Cd(IPDB)_2Cl_2]的合成及其晶体结构

以2-(4-二甲氨基苯基)咪唑[4,5-f]1,10-邻菲啰啉(IPDB)为配体,Cd Cl_2·2.5H_2O为镉源,用水热法合成了一个新型的镉配合物[Cd(IPDB)_2Cl_2,(1)],其结构和性能经FL,FT-IR,元素分析,X-射线单晶衍射和TG表征。1属斜方晶系,空间群Pbcn,晶胞参数a=14.933(12),b=8.349(7),c=31.93(3),α=γ=90°,β=90(4)°,V=3 981(6)~3,Dc=1.438 g·cm~(-3),Z=4,R_1=0.048 0,ωR_2=0.109 8。每个Cd分别与2个双齿螯合的IPDB中的一个N和2个Cl配位,形成畸变的八面体几何构型。在490 nm波长激发下,1的最大荧光发射峰位于569 nm。1的初始分解温度为495℃,失重为72.24%。     

5,6-2H-1,2,4-三唑[3,4-b][1,3,4]噻二嗪衍生物的合成及抗癌活性测定

取代苯甲醛与4-氨基-5-(3,4,5-三甲氧基苯基)-1,2,4-三唑-3-硫酮(2)缩合生成5-(3,4,5-三甲氧基苯基)-4-取代苯基亚胺基-1,2,4-三唑-3-硫酮(3),再烷基加成化为新型5,6-2H-1,2,4-三唑[3,4-b][1,3,4]噻二嗪衍生物4.化合物结构经1HNMR 13C NMR,IR以及元素分析确认.采用噻唑兰(MTT)比色法进行化合物抑制人体前列腺癌细胞(PC3)体外活性测试,结果表明所合成的化合物具有不同程度的抑制PC3活性,其中化合物4a在10μmol·L-1浓度下对PC3的抑制率为75.9%.