二茂铁的电合成及反应条件研究

以高纯度的环戊二烯(CPD)为原料,以金属铁为阳极,卤化盐作为导电盐,有机溶剂作为介质,在采用氮气保护的情况下电解合成二茂铁。对电解合成二茂铁的反应条件进行了优化研究,结果表明:电解液比例为二甲基亚砜(mL)∶环戊二烯(mL)∶溴化钠(moL)=10∶1∶0.008。实验分别以铁板和镍板作为工作电极和对电极,极板间距为1~1.5 cm,电解电压为3.2~5.2 V(vs.SCE),反应时间为5 h,反应温度为40℃,强烈搅拌条件下电解合成效率较高。     

四步法电解合成二茂铁新工艺的研究

本文采用高温解聚、电解合成、蒸发回收、高温升华等四步新工艺在工业上合成了二茂铁。产率９８％、纯度达到９８％以上，成本低廉，操作简单，利于工业化自动控制，具有很好的推广应用价值。     

二茂铁的合成

简要介绍了金属有机化合物二茂铁的性质及合成方法。     

二茂铁的合成

简要介绍了金属有机化合物二茂铁的性质及合成方法。     

合成乙烯基二茂铁的简易方法

乙烯基二茂铁的合成方法,以往是将二茂铁在磷酸等催化剂作用下与乙酸酐或乙酞氯反应合成单乙酰基二茂铁,分离后用氢化锂铝或硼氢化钠还原成a-二茂铁基乙醇,再经脱水制成乙烯基二茂铁。此方法按原始原料计算乙烯基二茂铁的产率很低。本文提出依据二茂铁在低温浓硫酸溶液中,与醛反应生成a-二茂铁正碳离子的反应机理,不经分离即可脱水,制得乙烯基二茂铁。该方法可使乙烯基二茂铁的产率大大提高。其反应式如下:     

电解法合成二茂铁体系中环戊二烯的阴极还原

用动电扫描法测定了环戊二烯在电解法合成二茂铁体系中的阴极极化曲线和循环伏安图，讨论了环戊二烯在不同电位区间的动力学控制步骤。表明在给定介质中环戊二烯的阴极还原动力学规律与过电位有关。     

二茂铁的电解合成及应用

二茂铁(Ferrocene)是一种有着广泛用途的金属有机化合物.自20世纪50年代首次发现以来,由于其特殊的化学结构,引起了众多化学家的兴趣,数百种的二茂铁衍生物被制备出来,并应用到各个领域之中.目前,合成二茂铁的主要方法是化学合成法和电化学合成法两种.阐述了二茂铁的性质、二茂铁及衍生物的应用、二茂铁的电解合成及影响因...     

环戊二烯稳定性及电解合成二茂铁后处理方法的研究

本文提出已解聚之环戊二烯其密度或折光率与环戊二烯单体含量（体积百分数Ｖ％）具有线性关系．由此可考察不同温度和时间条件下环戊二烯单体的稳定性。并提出首先抽滤电解液，滤液经减压蒸馏回收ＤＭＦ，可重复使用，每次电解补充量不超过５％，以核磁共振谱证实了回收效果良好，滤渣及蒸馏残渣经水汽蒸馏收集产物，其熔，久、元素分析结果及红外光谱图表明产物确为二茂铁。     

乙酰基二茂铁的合成

以三氯化铝为催化剂,乙酰氯为酰化剂,在二氯乙烷中对二茂铁酰化得到了产率较高的乙酰基二茂铁。研究了反应温度、加料方式和反应物摩尔比对反应的影响。     

Electrochemical synthesis of peroxomonophosphate using boron-doped diamond anodes

A new method for the synthesis of peroxomonophosphate, based on the use of boron-doped diamond electrodes, is described. The amount of oxidant electrogenerated depends on the characteristics of the supporting media (pH and solute concentration) and on the operating conditions (temperature and current density). Results show that the pH, between values of 1 and 5, does not influence either the electrosynthesis of peroxomonophosphate or the chemical stability of the oxidant generated. Conversely, low temperatures are required during the electrosynthesis process to minimize the thermal decomposition of peroxomonophosphate and to guarantee significant oxidant concentration. In addition, a marked influence of both the current density and the initial substrate is observed. This observation can be explained in terms of the contribution of hydroxyl radicals in the oxidation mechanisms that occur on diamond surfaces. In the assays carried out below the water oxidation potential, the generation of hydroxyl radicals did not take place. In these cases, peroxomonophosphate generation occurs through a direct electron transfer and, therefore, at these low current densities lower concentrations are obtained. On the other hand, at higher potentials both direct and hydroxyl radical-mediated mechanisms contribute to the oxidant generation and the process is more efficient. In the same way, the contribution of hydroxyl radicals may also help to explain the significant influence of the substrate concentration. Thus, the coexistence of both phosphate and hydroxyl radicals is required to ensure the generation of significant amounts of peroxomonophosphoric acid.     

Electrochemical synthesis of 2,2-dinitropropanol

This paper describes electrochemical approaches to the synthesis of 2,2-dinitropropanol (DNPOH) and discusses the potential for pilot-plant scale synthesis. In this work, the anode of the electrochemical cell replaces the chemical oxidants used in the conventional synthesis for the purpose of reducing secondary waste and the consequent disposal cost. The electrosynthesis reactions described in this work use the common starting material, nitroethane (NE). The synthesis of the end-product DNPOH involves two steps: (1) electrochemical oxidative nitration (addition of a geminal NO₂ group); and, (2) condensation with formaldehyde. Electrochemical oxidation of NE was first attempted by direct oxidation on a Pt electrode surface resulting in low yield and significant generation of undesirable by-product. Alternatively, two different mediators were employed resulting in a dramatic improvement of yield for the oxidative nitration step. The two different mediators used, Ag⁺/Ag⁰ and Fe(CN)₆^−3/−4, were derived from the chemical oxidants known to perform the oxidative nitration. The Fe(CN)₆^−3/−4 mediator demonstrated the best promise for scale-up and industrial production due to the lower cost of the mediator and the solubility of the mediator lending it to greater ease-of-use in conventional electrochemical cell designs.     

Electrochemical synthesis of melanin free-standing films

Free-standing melanin films were successfully synthesised electrochemically from dopa. The optimum synthetic conditions such as pH, concentration and current were determined, and it was found that free-standing films could only be formed when ITO glass electrodes were used. The films were analysed by solid state NMR and XPS which showed the presence of indolic moieties characteristic of melanin-type macromolecules. The film showed higher conductivity than chemically synthesised melanin previously reported in literature and also exhibited photoconductivity.     

以对甲苯磺酸为催化剂合成羟基二氢双环戊二烯

本文主要考察了以对甲苯磺酸为催化剂,双环戊二烯经过水合制得羟基二氢双环戊二烯。通过正交试验考察了蒸馏水/双环戊二烯（摩尔比）,反应时间,反应温度及对甲苯磺酸（质量比）等主要因素对实验的影响,确立了最佳的工艺条件为：蒸馏水/双环戊二烯（摩尔比）为10：1,反应时间是9小时,反应温度是100℃,对甲苯磺酸质量分数是1%。在此条件下产品收率可达到83%,经减压蒸馏之后物质纯度可达到97%。并对所得到的产品进行折光率测定和红外谱图表征,确定为目的产品。     

以对甲苯磺酸为催化剂合成羟基二氢双环戊二烯

本文主要考察了以对甲苯磺酸为催化剂,双环戊二烯经过水合制得羟基二氢双环戊二烯。通过正交试验考察了蒸馏水,双环戊二烯（摩尔比）,反应时间,反应温度及对甲苯磺酸（质量比）等主要因素对实验的影响,确立了最佳的工艺条件为：蒸馏水,双环戊二烯（摩尔比）为10：1,反应时间是9小时,反应温度是100℃,对甲苯磺酸质量分数是1％。在此条件下产品牧率可达到83％,经减压蒸馏之后物质纯度可达到97％。并对所得到的产品进行折光率测定和红外谱图表征,确定为目的产品。     

Magnetite nanoparticles: Electrochemical synthesis and characterization

Magnetite (Fe₃O₄) nanoparticles (NP) with sizes between 20 and 30 nm have been obtained by Fe electrooxidation in the presence of an amine surfactant, which acted as a supporting electrolyte and coating agent, controlling particle size and aggregation during the synthesis. The effect of different parameters on the nature and size of the particles as well as the mechanism of formation of the particles have been studied by different techniques. It was concluded that, under the electrochemical conditions used in this work, the NP mean size was found to be constant at around 20 nm when the electrooxidation current density is increased from 10 to 200 mA cm⁻². However, when the potential is over 6 V, particle size decreases from 30 to 20 nm and metallic iron appears as an impurity. The mechanism of particles formation has being clarified and the critical effect of the distance between electrodes for obtaining magnetic iron oxide nanoparticles has been understood. Finally, the presence of an electrostatic adsorbed surfactant coating the particles allows the functionalization of the particles easily by exchange reaction with biomolecules of interest, which makes this material very promising for future application in biotechnology.     

异烟酸的电化学合成及示波极谱法测定

以钛基二氧化铅电极（Ti/PbO2)为阳极,在硫酸水溶液介质中,电解氧化4－甲基吡啶合成异烟酸。最佳合成条件：硫酸浓度为2.80mol/L,4-甲基吡啶浓度为0.60mol/L,电解电流密度为80mA/cm^2,温度60℃。在此条件下,4－甲基吡啶的转化率为64．6％,电流效率67％。产物纯度为97．7％。     

电化学生产五氧化二氮的研究进展

对Ｎ２Ｏ５的用途及制备方法作了概括说明,探讨了电解法制备Ｎ２Ｏ５的方法及工艺,简要介绍了国外的Ｎ２Ｏ５生产的发展动态。     

Electrochemical production of alkoxy-substituted phenols

The electrochemical oxidation of hydroquinone and substituted hydroquinones has been studied over graphite and platinum electrodes in different alcohol media. The results have shown that good yields of the corresponding alkoxy-substituted phenols can be obtained with high selectivities towards the hydroquinone monoalkyl ether. A mechanism is put forward to explain the formation of the alkoxyphenol through the creation of a quinhydrone complex, formed between the hydroquinone and benzoquinone, which is then attacked by the alcohol acting as a nucleophile.In this study, the effect of sulfuric acid as supporting electrolyte and acid catalyst was compared with that of methanesulfonic acid. It was found that sulfuric acid gave the best yield for different alkoxyphenols. The alcohols under investigation were C₁-C₈, and it was found that the longer the chain length of the alcohol, the slower the tendency to produce alkoxyphenols. Branched alcohols such as secondary and tertiary alcohols showed no reactivity towards the quinhydrone complex. Some of the yields obtained are as follows: 4-methoxyphenol (97%), 4-ethoxyphenol (71.4%) and 4-propoxyphenol (81.1%).     

Electrochemical synthesis of selenium nanotubes by using CTAB soft-template

The single-crystalline Se nanotubes were synthesized on the surface of Au sheet electrode by cyclic voltammetry. In synthesis process, cetyltrimethyl ammonium bromide (CTAB) was used as soft-template. The formation mechanism of Se nanotubes was discussed. Furthermore, the deposits with other morphologies were also obtained by modulating parameters in the synthesis process. The products as-prepared were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and laser Raman spectrograph (LRS). The electrochemical behavior of the Se nanotubes was studied by the linear scan voltammetry.