有机电合成发展应用

有机电合成是一门涉及电化学、有机合成及化学工程的交叉学科。本文概述了有机电氧化反应、有机电还原反应、间接有机电合成、金属有机化合物电合成及特殊有机电合成方面的应用进展，并简要介绍了超声、超临界、光和磁场及仿生等技术与有机电合成融合发展的最新动向。     

芳醛电合成技术研究进展

阐述了有机电合成的发展概况，详细介绍了在主要电合成技术（直接电合成、间接电合成以及成对电合成）在芳醛电合成中的应用。     

间接电氧化的进展

:阐述了间接电氧化的进展。阳极间接电氧化 ,重点介绍以Mn3 + /Mn2 + 和Ce4 + /Ce3 + 作电解媒质的研究结果。阴极间接电氧化 ,重点介绍以WO52 -/WO4 2 -和VO(acac) 2 OOH/VO(acac) 2为电解媒质的研究结果。     

有机电合成技术概况（续）

5.间接电合成5.1 阳极氧化工艺5.1.1 环氧丙烷环氧丙烷的电合成是间接利用阳极氧化反应来制取有机化合物的最典型例子之一。Kellog 公司在这方面进行了大量的技术开发工作。他们采用的基本方法是,在氯化钠水溶液中通入丙烯并进行电解。由于 Cl~-在阳极放电生成 Cl_2,Cl_2又在该电解液中与水     

苯甲醛系列化合物的电合成进展

本文介绍了苯甲醛系列化合物的三种电合成方法：苯环上丙烯基、羟基和甲基的阳极氧化,苯环上羧基的阴极还原,苯环上甲基的阳极取代。着重对甲基的阳极氧化过程中运用的新技术及发展趋势作了评述。     

由甲苯成对电合成苯甲醛的研究

本文研究了以甲苯为原料,采用成对电解合成方法,进行阴极和阳极同时间接电氧化制取苯甲醛。当选用钛基镀铂电极及钒与锰氧化还原电对时,成对电合成苯甲醛的总电流效率达179.5％。还研究了添加CTAB对化学氧化速度的影响,以及外加H_2O_2对阴极电合成选择性的影响。     

间接有机电合成原理及应用：Ⅲ.间接阴极还原电合成

本文根据使用的媒质，分别介绍了还原系，还原活性金属氧化还原系，还原活性有机化合物氧化还原系，过氧化物等作媒质的间接阴极还原电合成的应用状况。     

苯甲醛电合成技术的新进展

简述了苯甲醛电合成的发展概况,详细地介绍了间接电合成法、成对电合成法和超声电合成法3种苯甲醛合成技术,并着重介绍了Mn3+/Mn2+电解媒质作为氧化还原电对间接电合成苯甲醛的应用情况,指出超声电合成法将是合成苯甲醛很有前景的方法。     

表面活性剂在有机电合成中的应用

主要讲述了表面活性剂在有机电合成中的作用和最近的研究情况。将有机电合成分为间接电合成和直接电合成两部分，简单介绍了表面活性剂在间接电合成中的作用和作用机理，着重介绍了表面活性剂在直接电合成中的应用情况、作用机理以及如何选择合适的表面活性剂。最后提出了表面活性剂的研究方向。     

成对电解同时合成丁二酸和乙醛酸

研究了成对电解新工艺，即在阳极室乙二醛电氧化合成乙醛酸，收率超过７０％；在阴极室顺丁烯二酸电还原合成丁二酸，收率可达８５％。同一电解槽同时获得二种高附加值的产品，并且比旧工艺节约了４０％的电能。该工艺具有投资少，工艺简单，而且无三废排放的特点     

间接电合成槽型结构的研究

研究了Ce4+/Ce3+做氧化媒质间接电合成芳香醛的槽型结构。结果表明,隔膜电解槽与无隔膜电解槽相比,电解收率高6 8%,电流效率高6 6%;在无隔膜电解槽内,槽压低0 85V,通过调节阴阳极面积比,减少在阳极区Ce3+电解氧化生成的Ce4+在阴极区被还原为Ce3+,电耗比隔膜电解槽减少70 6kW·h/t,生产对甲氧基苯甲醛电耗减少590kW·h/t。     

对有机电合成的原理及应用

本文综述了国内外成对有机电合成的新研究进展,根据电解合成的方式即电解过程是否需要媒质的情况对成对有机电合成进行了新的分类,介绍了这二类有机成对电合成的原理和应用情况,并对它们的特点进行了评述。成对有机电合成的不断发展,为有机化合物的合成开辟了新的途径,并将推动绿色工业的进步,其应用将会有更广阔的前景。     

A homogeneous redox catalytic process for the paired synthesis of l-cysteine and l-cysteic acid from l-cystine

Redox catalytic process involved in the paired electrosynthesis of l-cysteine and l-cysteic acid from l-cystine is investigated by cyclic voltammetric technique and also confirmed by preparative electrolysis. The cyclic voltammetric behaviour shows that in the catholyte, in situ deposited tin (Sn) surface acts as a redox catalyst for the electro-reduction of l-cystine to l-cysteine whereas in the anolyte, the electro-generated bromine acts as a homogeneous redox mediator to enhance the electro-oxidation of l-cystine. l-Cysteine hydrochloride monohydrate (l-cysteine) and l-cysteic acid are prepared from l-cystine by preparative electrolysis with high purity and high yield using graphite cathode and DSA anode. At optimum concentration of l-cystine with 1:1 concentration ratio (catholyte:anolyte), the material yield obtained for l-cysteine is above 80% and that for l-cysteic acid is close to 60% in the paired electrosynthesis process in the batch operation. Scope for further experiments in conversion efficiency is also discussed.     

以四碳不饱和酸为原料成对电合成1,2-二醇类化合物

建立了一种成对电合成体系 ,以VO(acac) 2 VO(acac) 2 OOH为媒质 ,间接氧化烯烃得到相应的环氧化物 ;阳极以Br2 Br- 为媒质 ,间接氧化烯烃成邻溴代醇。马来酸环氧化反应总电流效率高达 145 %     

Properties and applications of electrodes covered with a porous diaphragm—2. Theoretical and practical aspects of electrosynthesis in single compartment electrolysis cells

The use of porous coverings on the counterelectrode for the reduction of the rate of loss reactions in single compartment electrolytic reactors has been studied. The theoretical current efficiencies for various overall reaction schemes have been calculated. The method has been tested for the electrosynthesis of potassium permanganate, ceric sulphate and sodium hypochlorite. Considerably improved reactor performance was realised. The experimental performance was in accord with that calculated theoretically.     

Cathodic crossed hydrocoupling XIII. Synthetic aspect of the cathodic crossed hydrocoupling reaction of aliphatic carbonyl compounds with electrophiles in aqueous sulfuric acid

For the purpose of organic electrosynthesis, the cathodic crossed hydrocoupling of aliphatic carbonyl compounds with some electrophiles was investigated. When mixtures of carbonyl compounds (such as ketone and aldehyde) and electrophiles (such as activated olefin, pyridine, and cyanamino compound) were electrolysed with various kinds of cathodes in aqueous sulfuric acid, these compounds were coupled reductively to give many useful products in the field of synthetic organic chemistry. In most of the couples of carbonyl compounds and electrophiles, the reduction potentials of the formers were more positive than those of the latters under the electrolysis condition. The yield, current efficiency, and selectivity of products depended on electrolytic conditions, especially cathode material.     

Ce~(4+)/Ce~(3+)做氧化媒质间接电合成邻氯苯甲醛

用硫酸做介质、Ce4 + Ce3+ 做氧化媒质间接电合成邻氯苯甲醛。通过正交实验和单因素实验确定出最佳工艺条件为 :反应温度 348K ,表面活性剂浓度 1 .4× 1 0 - 3～ 2 .2× 1 0 - 3mol L ,硫酸浓度 7.5mol L。在优化的实验条件下邻氯苯甲醛的产率达 93.1 % ;在相应的电解实验中 ,电流效率为 89.46% ,电解收率为 50 .1 5%。     

SPEEK复合膜在电解制备过硫酸铵中的应用

为达到减少电解制备过硫酸铵的能耗及提高电流效率的目的,从改良电解槽隔膜的角度出发,分别对几种自制复合膜的电解性能进行了考察和比较,并对它们的机械强度和支撑层的耐腐蚀性进行了测试。通过试验发现：聚酯滤布的耐电解液腐蚀性最好;以100目聚酯滤布为支撑层制得的磺化聚醚醚酮（SPEEK）复合膜机械强度最高;以50目聚酯滤布为支撑层制得的SPEEK复合膜的电流效率最高且单位电耗最低。综合考虑,以50目聚酯滤布为支撑层制得的SPEEK复合膜比较适合应用于电解制备过硫酸铵中,尽管它的机械强度不是最大,但是与不添加支撑层的纯SPEEK膜相比其机械强度有了明显的提高,而且具有较高的电流效率和比较小的能耗。     

Electrolytic preparation of 2-osuloses: a route to L-ascorbic acid

Conclusions Indirect electrosynthesis of 2-osuloses from aldopentoses and ketohexoses has shown to be an interesting tool for reducing the amount of chemical oxidant (copper (II) involved in the reaction. However, the experimental conditions under which the reaction is carried out are far from those industrially acceptable. Nevertheless, the potential advantages of the electrolytic method, as well as its interest in organic synthesis, are so important that further effort should be spent in studying this procedure.