苯并咪唑及其衍生物合成与应用研究进展

苯并咪唑及其衍生物具有良好的生物活性, 而且是一种重要的药物中间体. 由于它们具有良好的生物活性和反应活性, 一直都是研究的热点. 从该类化合物的合成与应用两个方面综述了近年来该领域的重要研究成果.     

甲基酮香料的仿生合成新方法研究

四氢叶酸辅酶在生物体内的作用是转移不同氧化态的一碳单元, 当一碳单元处于甲酸氧化态时, 活性部位是具有五元环状结构的咪唑啉环. 模拟四氢叶酸辅酶转移一碳单元的反应, 以苯并咪唑甲基碘盐作为四氢叶酸辅酶甲酸氧化态模型, 以格利雅试剂甲基碘化镁作为接收一碳单元的亲核试剂, 将甲酸氧化态的一碳单元转移给甲基碘化镁, 成功合成了三种重要的甲基酮香料甲基己基酮、甲基壬基酮和甲基十一烷基酮, 其结构用元素分析, 1H NMR, IR和MS等方法进行了表征, 并对反应机理和反应条件进行了讨论, 为甲基酮香料提供了一种仿生合成新方法.     

Hydrothermal Synthesis,Crystal Structure and Fluorescence Spectrum Studies of a Supramolecular Compound {[2-（2-Pyridyl）benzimidazoleH2]2＋ ·[SbCls]2-}2

A new supramolecular compound, { [2-（2-pyridyl）benzimidazoleH2]2＋.[SBC15]2-}2, was synthesized by the hydrothermal reaction of o-diaminobenzene, 2-pyridinecarboxylie acid and SbCl3 in 1：1 HC1 solution, and characterized by chemical analysis, elemental analysis, IR spectra, thermogravimetfic analysis and fluorescence spectra. The crystal structure was deter- mined by X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group P211c, with a = 16.0397（13）, b = 14.3189（12）, c = 15.6370（13） A, β = 105.8980（10）°, V = 3454.0（5） A3, Z = 4, C24H22Cl10N6Sb2, Mr = 992.48, Dc = 1.909 g/cm3,/z = 2.366 mm-1, S = 1.010, F（000） = 1920, R = 0.0254 and wR = 0.0555. The coordination anion, [SbCl5]2- which is a distorted tetragonal pyramid, is composed by coordinating action with Sb3＋ ion and five adjacent chloride ions. Every four coordination anions of [SbCl5]2- form a biquaternion ring structure through the secondary bonding of Sb...Cl. Moreover, the compound adopts a three-dimensional network supramolecular structure because of the hydrogen bonds and π-π stacking between the rings and the 2-（2-pyridyl）benzimidazole divalent cations. The title compound also shows good fluorescent behaviors.     

Hydrothermal Synthesis, Crystal Structure and Fluorescence Spectrum Studies of a Supramolecular Compound {[2-(2-Pyridyl)benzimidazoleH2]2+·[SbCl5]2-}2

A new supramolecular compound, {[2-(2-pyridyl)benzimidazoleH2]2 ·[SbCl5]2-}2, was synthesized by the hydrothermal reaction of o-diaminobenzene, 2-pyridinecarboxylic acid and SbCl3 in 1:1 HCl solution, and characterized by chemical analysis, elemental analysis, IR spectra, thermogravimetric analysis and fluorescence spectra. The crystal structure was deter- mined by X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group P21/c, with a = 16.0397(13), b = 14.3189(12), c = 15.6370(13) (A), β = 105.8980(10)°, V = 3454.0(5) (A)3, Z = 4, C24H22Cl10N6Sb2, Mr = 992.48, Dc = 1.909 g/cm3, μ = 2.366 mm-1, S = 1.010, F(000) = 1920, R = 0.0254 and wR = 0.0555. The coordination anion, [SbCl5]2- which is a distorted tetragonal pyramid, is composed by coordinating action with Sb3 ion and five adjacent chloride ions. Every four coordination anions of [SbCl5]2- form a biquaternion ring structure through the secondary bonding of Sb…C1.Moreover,the compund adopts a three-dimensional network supramolecular structure because of the hydrogen bonds and π-π stacking between the rings and the 2-(2-pyridy1)benzimidazole divalent cations.The title compound also shows godd fluorescent behaviors.     

N-取代苯基-N′-(2-苯并咪唑甲酰基)脲的合成及抑菌活性

许多芳酰基脲类化合物具有良好的杀虫活性,有些还具有一定的杀菌、除草、植物生长调节等生物活性,已成为农药研究和开发的热点[1,2].     

2-取代苯并眯唑合成工艺的改进

以邻苯二胺和有机酸为原料,在磷酸和多聚磷酸混合酸的催化下合成了四种2-取代苯并咪唑化合物。利用红外光谱、核磁氢谱、熔点测定等方法对产物进行了结构表征。讨论了反应温度、催化剂用量对收率的影响。该合成工艺较原有的工艺得以完善,收率有较大提高。     

An antibacterial silver(I) supramolecular network assembled from thiophene-2,5-dicarboxylate and benzimidazole

Abstract

A silver(I) supramolecular network Ag(BIm)₂(HTDC) (1) was assembled from thiophene-2,5-dicarboxylic acid (H₂TDC) and benzimidazole (BIm) ligands and characterized by single-crystal X-ray diffraction, elemental analysis, FT-IR, and thermal gravimetric analysis. Complex 1 possesses a two-dimensional structure with a hydrogen-bonded grid network, in which the adjacent [Ag(BIm)₂]⁺ cations and (HTDC)^– are bridged via N–H···O hydrogen bonds forming undulating ribbons. The antibacterial properties of 1 were investigated by determining the minimal inhibitory concentration (MIC), the growth curve of bacteria and zone inhibition value assays against Gram-negative bacterium, Escherichia coli, and Gram-positive bacterium, Staphylococcus aureus. The MIC of 1 against E. coli and S. aureus are 15-20?ppm and 20-30?ppm which showed that 1 has higher antibacterial activity than commercial silver nanoparticles. The mechanism of antibacterial activity of 1 was also discussed.     

Theoretical Study on Excited-State Intramolecular Proton Transfer of 2-（2＇-Aminophenyl）benzimidazole Derivatives： Substituent EffectE-C=O or E-OSi. The K＊ configuration become more stable than E＊ in S~ state when substitutent is E-CC, E-NH, E-CO, E-...

研究了2-（2’-氨基苯基）苯并咪唑（APBI）氨基中一个H被CH3（E-C）,Sill3（E-OSi）,NH2（E-N）,COH（E-CO）,N02（E-N02）,CF3（E-F）,CN（E-CN3）,OMe（E-OMe）,COCH3（E-CC）,Ts（E-S）,P-CH3C6H4CO（E-C=0）和P-CH3C6H4NHCO（E-NH）取代后,其基态及激发态分子内质子转移（ESIPT）性质的变化规律．结果表明各衍生物基态最稳定构型为烯醇式构型E,次稳定构型旋转异构体R,酮式构型K只有当取代基为E-CN3,E-F,E-N02,E-N,E-OMe和E-S时才存在．基态各环的核独立化学位移（NICS）研究表明取代基的引入会影响APBI环电子离域性．所有APBI衍生物都能发生激发态分子内质子转移,当引入取代基为E-CN3,E-N或E-OMe时,所得的APBI衍生物S1态分子内质子转移是无能垒过程;引入取代基为E．c,E．C=O或E．OSi时,对APBI的ESIPT势能面基本无影响,而当取代基为E-CC,E-NH,E-CO,E-F,E-N02和E-S时,使得Sl态APBI的K’构型能量低于E     

Enhancement of properties of polyimide/silica hybrid nanocomposites by benzimidazole formed hydrogen bond

Polyimide/silica hybrid nanocomposites were prepared by sol–gel method without coupling agent. A novel diamine with a benzimidazole group, 2‐(4‐aminophenyl)‐5‐aminobenzimidazole (PABZ), was introduced to copolymerize with 4,4'‐oxydianiline (ODA) and pyromellitic dianhydride (PMDA) to synthesize polyimide (PI) matrix. The compatibility between PI and silica was improved by hydrogen bonds formed between silica phase and the –NH– group on benzimidazole of the new diamine. Highly transparent hybrid films were obtained when silica content reached as high as 30 wt%. SEM results show that silica particles with sizes much smaller than that in PMDA‐ODA/silica system disperse homogeneously in the PI matrix. Differing from most hybrid systems without coupling agent, the tensile strength of PABZ system increases from 152 MPa to 165 MPa with silica content increasing from 0 to 20 wt%, while, it decreases linearly in PMDA‐ODA system. DMA analysis shows that the introduction of PABZ largely increases the glass transition temperature (Tg) for all silica contents, which is suggested to be due to the more rigid structures and stronger interaction between the two phases. Meanwhile, the decomposition temperature and char yields at 800 °C are both higher than that of pure PIs. The structures of the hybrid films were identified by FTIR spectra, which indicate that different silica morphologies are developed, resulted from the hydrogen bonds between benzimidazole and silica phase. Copyright © 2011 John Wiley & Sons, Ltd.     

合成苯并咪唑类化合物的工艺改进

邻苯二胺磷酸盐与脂肪酸在无溶剂的条件下回流反应合成了苯并咪唑类化合物,其结构经IR确证。正交试验确定最佳反应条件为:邻苯二胺50 mmol,n(邻苯二胺):n(甲酸)=1.0:1.5,磷酸4 g,回流反应7 h。在最佳反应条件下做放大实验,产率89.3%。