硝基苯并咪唑衍生物的合成、表征及抑茵活性的测定

以苯并咪唑为原料，经硝化、二茂铁磺酰化等步骤，合成了8种未见文献报道的硝基苯并咪唑衍生物，其结构经MS，^1H NMR和元素分析确证．由于硝基苯并咪唑的互变异构，二茂铁磺酰化后，产生两个异构体，用X射线衍射仪测定了化合物2a的晶体结构．初步的抑菌实验结果表明，该系列化合物具有良好的抑菌作用，其抑菌活性均优于对照药剂50％多菌灵可湿性粉剂．     

二茂铁磺酰基苯并咪唑衍生物的合成、表征及晶体结构

以苯并咪唑为原料，经硝化、二茂铁磺酰化，合成了六种未见报道的二茂铁磺酰基硝基苯并咪唑衍生物，其结构经元素分析、质谱、核磁共振确证。由于苯并咪唑的互变异构，经二茂铁磺酰化后，产生两个异构体，通过X射线衍射，测定了异构体的晶体结构。     

6-硝基苯并咪唑杂环衍生物的合成

以６－硝基苯并咪唑－１－乙酰肼和５－（６－硝基苯并咪唑－１－亚甲基）－３－巯基－４－氨基－１,２,４－三唑为原料,在不同条件下合成了一系列新的均三唑〔３,４－ｂ〕－１,３,４－噻二唑,１,２,４－三唑和１,３,４－恶二唑衍生物。化合物的结构均经元素分析、＾１Ｈ ＮＭＲ、ＩＲ和ＭＳ确证,并对其波谱性质进行了讨论。     

4,5-二苯基-2-取代基-1-磺酰基咪唑的合成

用多种磺酰氯或磺酸酐与4,5-二苯基-2-取代-1-磺酰基咪唑负离子反应, 合成了10个未见文献报道的1-磺酰基咪唑类化合物. 所有化合物均经1H NMR和13C NMR确证.     

三苯基氧膦和三氟磺酸酐参与的二茂铁咪唑啉合成

二茂铁咪唑啉可以有效地从二茂铁羧酸出发合成．二茂铁羧酸和乙二胺衍生物反应制得的二茂铁酰胺，在三苯基氧膦和三氟磺酸酐所形成的锛盐作用下有效地脱水得到二茂铁咪唑啉化合物．该反应条件温和、反应快、产率高，为二茂铁咪唑啉化合物提供了一个有效的合成方法．     

咪唑并吡啶化合物的合成研究进展

咪唑并吡啶类化合物是一类非常重要的含氮稠杂环化合物, 在医药、农药和染料工业有着广泛的应用. 该类化合物由于其特定的生理活性以及和吲哚、氮杂吲哚等在结构上的类似性, 引起了人们广泛的兴趣. 常见的咪唑并吡啶类化合物有咪唑并[1,2-a]吡啶、咪唑并[1,5-a]吡啶、咪唑并[4,5-b]吡啶和咪唑并[4,5-c]吡啶等类型. 以咪唑并[1,2-a]吡啶和咪唑并[1,5-a]吡啶化合物为例, 阐述该类化合物近十年来的合成研究进展.     

含二茂铁基的咪唑啉酮类化合物的合成与生物活性

含二茂铁基的咪唑啉酮类化合物的合成与生物活性     

功能性二茂铁单、双乙基咪唑的合成

以单、双乙酰基二茂铁为原料,经还原和脱水反应,高效地合成了单、双齿功能性配体--二茂铁乙基咪唑和二茂铁双乙基咪唑,其结构经1H NMR,IR,MS和元素分析表征.     

新型非对称1,1＇-双取代咪唑二茂铁的合成

以二茂铁为原料,通过Friedel-Crafts烷基化反应、Vilsmeier-Haack反应等合成了12个新型1-取代咪唑二茂铁与非对称1,1’-双取代咪唑二茂铁,其结构经1H NMR,IR和ESI-MS表征。     

2,4,6-三硝基苯腙的合成及其抑菌活性

三硝基氯苯与水合肼反应,直接合成了2,4,6-三硝基苯肼(2),2与醛、酮试剂反应合成了6个新的苯腙化合物,其结构经1H NMR,IR和元素分析表征。抑菌试验表明,部分目标产物具有良好的抑菌活性。     

二茂铁席夫碱的合成及细胞毒活性

为了研究二茂铁席夫碱对癌细胞毒性,以二茂铁甲醛或乙酰基二茂铁与3-取代-4-氨基-1,2,4-三唑-5-硫酮或酰肼缩合,得到6个新型的含二茂铁基的缩胺类席夫碱和4个酰腙类席夫碱.利用1H NMR,IR,MS谱和元素分析对化合物结构进行了表征.体外细胞测试结果表明,所有化合物对Hela (宫颈癌细胞)均有一定的抑制生长活性,而且杂环缩胺类席夫碱2的细胞毒活性要强于酰腙类席夫碱4.     

1,1′-二硒取代二茂铁衍生物的合成

由1,2,3-三硒[3]桥二茂铁(Ferrocenophane)经LiAlH_4还原生成二硒酚,不经分离直接与一亲电试剂在三乙胺存在下反应,得到7种1,1′-二硒醚二茂铁,4种1,n-二硒[n]桥二茂铁(n=3～5)和1种螺形化合物[Fe(C_5H_4Se)_2]_2Sn。这12种化合物中有7种尚未见文献报道,对其中几种产物进行了~(77)Se NMR谱及质谱分析。讨论了影响产率的因素和核磁共振图谱。     

Design,Synthesis, and Biological Evaluation of Novel 1,3,4‐Thiadiazolylpyrazolines Compounds Containing Ferrocene

The synthesis of 1,3,4‐thiadiazole skeleton compounds exhibiting high fungicidal activities has been demonstrated. Thirteen novel 1,3,4‐thiadiazolyl‐pyrazolines compounds containing ferrocene were designed and synthesized from the ferrocenylchalcones intermediates 3a – 3m and the 2‐hydrazino‐5‐phenyl‐1,3,4‐thiadiazole intermediate 8 . All compounds were characterized by ¹H NMR, ¹³C NMR, FT‐IR spectra, and HR‐MS, and the structure of one of the new compounds N‐(4‐phenyl‐1,3,4‐thiadiazol‐2‐yl)‐3‐ferrocenyl‐5‐phenyl‐pyrazoline 9a was further determined by X‐ray diffraction analysis. The preliminary results of a biological activity assay indicated that all the title compounds exhibited significant fungicidal activities against Pythium solani, Gibberella saubinetii, and Gibberella nicotiancola. Furthermore, compounds 9e and 9h displayed even higher fungicidal activities against the three fungal species compared with the control drug pyraclostrobin.     

Synthesis and biological evaluations of some Schiff-base esters of ferrocenyl aniline and simple aniline

The synthesis and biological studies of some long chain esters containing Schiff bases and their ferrocenyl analogues were carried out. The 4-amino ferrocene was prepared by the reported method. Long chain esters were synthesized by the condensation of different aliphatic acids with the corresponding aldehyde. The esters were then reacted with aniline as well as with 4-aminophenyl ferrocene to give corresponding Schiff bases. All the synthesized compounds were analyzed by elemental, FTIR and proton NMR studies, were also investigated for a range of biological activities. Determined by crown gall tumor inhibition assay. Antioxidant and DNA protective activities were determined by DPPH free radical scavenging assay and OH radical induced oxidative DNA damage assay, respectively. Among all test compounds, o-hydroxy-p-n-octadecanoyloxy-benzylidine-p-ferrocenyl aniline (FA2.1: a ferrocene containing Schiff base) showed highest antitumor, DPPH free radical scavenging and DNA protective activities.     

Synthesis,structure and biological activity studies of 2‐[(1H‐1,2,4‐triazol‐1‐yl)methyl]‐1‐aryl)‐3‐ferrocenyl prop‐2‐en‐1‐one derivatives

Fifteen new ferrocene derivatives containing 1H‐1,2,4‐triazole moiety were synthesized in various yields by the condensation of ferrocenecarboxaldehyde with 1‐aryl‐3‐(1H‐1,2,4‐triazo‐1‐yl)‐propen‐1‐ones in toluene. Their structures have been confirmed by ¹H NMR, IR, MS and elemental analysis. In addition, the crystal structure of 4l was determined. The antifungal and plant growth regulatory activities of the title compounds are discussed. Copyright © 2005 John Wiley & Sons, Ltd.     

Ferrocenophanes with Interannular Nitrogen–Gallium Bridges. 1,3,2‐Diazagalla‐[3]Ferrocenophanes and an 1‐Aza‐3‐Azonia‐2‐Gallata‐[3]Ferrocenophane. Synthesis and Structure

1,1′‐Bis(trimethylsilylamino)ferrocene reacts with trimethyl‐ and triethylgallium to give the μ‐[ferrocene‐1,1′‐diyl‐bis(trimethylsilylamido)]tetraalkyldigallanes. These were converted into the 1,3‐bis(trimethylsilyl)‐2‐alkyl‐2‐pyridine‐1,3,2‐diazagalla‐[3]ferrocenophanes, of which the ethyl derivative was characterized by X‐ray structural analysis. Treatment of gallium trichloride with N,N′‐dilithio‐1,1′‐bis(trimethylsilylamino)ferrocene affords μ‐[ferrocene‐1,1′‐diyl‐bis(trimethylsilylamido)]tetrachlorodigallane along with bis(trimethylsilyl)‐2,2‐dichloro‐1‐aza‐3‐azonia‐2‐gallata‐[3]ferrocenophane as a side product, and both were structurally characterized by X‐ray analysis. The solution‐state structures of the new gallium compounds and aspects of their molecular dynamics in solution were studied by NMR spectroscopy (¹H, ¹³C, ²⁹Si NMR).     

Synthesis,crystal structure,electronic spectroscopy,electrochemistry and biological studies of carbohydrate containing ferrocene amides

A series of four new ferrocene–carbohydrate amides was prepared from pentose and hexose sugar derivatives. These include (5‐amino‐5‐deoxy‐1,2‐O‐isopropylidene‐α‐d ‐xylofuranose)‐1‐ferrocene carboxamide (2a), (5‐amino‐3‐O‐benzyl‐5‐deoxy‐1,2‐O‐isopropylidene‐α‐d ‐xylofuranose)‐1‐ferrocene carboxamide (2b), (methyl‐6‐amino‐6‐deoxy‐2,3‐O‐isopropylidene‐β‐d ‐ribofuranoside)‐1‐ferrocene carboxamide (2c) derived from furanose sugars and (6‐amino‐6‐deoxy‐1,2:3,4‐di‐O‐isopropylidene‐α‐d ‐galactopyranose)‐1‐ferrocene carboxamide (2d) derived from pyranose sugar. The compounds were characterized by spectroscopic means and the structure of amide derived from α‐d ‐xylofuranose (2a) was determined by X‐ray crystallography. The electronic and optical properties of the compounds were studied by means of cyclic voltammetry and absorption spectroscopy. The UV and electrochemical studies of these compounds, performed in aqueous solutions under physiological conditions (at pH 7.4), confirmed their stability. These results indicated that the compounds were suitable for conducting biological studies. The CD spectral analysis displays the effect of sugar substituents on the compounds. The cytotoxicity and antimicrobial activity of these conjugates were investigated on different cancer cell lines and microbes respectively. The degree of inhibition varied over a broad spectrum of Gram‐ positive and Gram‐negative bacteria. In addition, the compounds also exhibited antioxidant properties. Copyright © 2012 John Wiley & Sons, Ltd.     

Contributions to the synthesis of some ferrocene-containing antibiotics

This Review discusses the synthesis and characterization by our Group of new antibiotics belonging to the class of penicillins, cephalosporins and rifamycins with ferrocenyl and 1, 1′-ferrocenilene residues in the molecule. As reactants for 6-aminopenicillanic acid (6-APA) and 7-aminocephalosporanic acid (7-ACA) the following were used: 1, 1-bis(chlorocarbonyl)ferrocene, ferrocenyl sulfochloride, 1, 1′-ferrocenylenedisulfochloride and thioglycolic acids S-modified with ferrocene. In the synthesis of rifamycins, the hydrazides of the thioglycolic acids, S-modified with ferrocene, were employed as nucleophilic agents. The synthesized intermediates were characterized by elemental analysis, TLC, IR, UV and ¹H NMR spectra. The characterization of new antibiotics was made by TLC, IR and UV spectral analysis. Biological activity was tested on Gram-negative and Gram-positive bacteria. Good activity is reported towards Gram-positive bacteria in the case of derivatives containing residues of thioglycolic acid S-modified with ferrocene, the antibacterial activity being similar to that of amoxicillin, carbenicillin and cephalothin. All compounds are inactive towards Gram-negative bacteria.     

Synthesis and combustion catalytic activity of ferrocene-based energetic compounds

Ammonium perchlorate (AP) is a common oxidizer in composite solid rocket propellants due to its excellent burning characteristics, good processability, and storability. Owing to their outstanding catalytic effects, ferrocene, and its derivatives have become the most widely used burning rate catalysts (BRCs). The addition of ferrocene and its derivatives to AP rendered performance optimization. In this study, azole-based ferrocenyl compounds were successfully synthesized. The compounds were characterized by single-crystal X-ray diffraction, UV-vis spectroscopy, and other techniques. The thermal degradation of AP catalyzed by these compounds was evaluated by differential scanning calorimetry and thermogravimetric analysis. Results revealed that the decomposition peak temperature of AP dramatically decreases and that the released heat of AP significantly increases with the new compounds as additives. Hence, the six azole-based ferrocenyl BR catalysts are favorable for the combustion catalytic activity.     

Synthesis of 2-Ferrocenyl-2-(Dialkyl Hydroxymethyl)D-1,3-Dithianes

The reactions of lithiated 2-ferrocenyl-1,3-dithiane with alkyl carbonyl compounds are studied. Fifteen of title compounds which are new ferrocene derivatives were synthesized and structurally characterized by elemental analysis, IR and 1H NMR spectra. The 1H NMR spectra of the dithiane compounds are briefly discussed.