Electrosynthesis of 5-amino-4-oxopentanoic acid hydrochloride

The electroreduction of methyl 5-nitro-4-oxopentanate was studied by means of a polarographic method and preparative electrolysis in acidic-alcoholic solutions. The effects of the following factors on the yield and quality of 5-amino-4-oxopentanoic acid hydrochloride were studied: the cathode material, amount of electricity, temperature, nature of the solvent, concentrations of the initial nitro compound and hydrochloric acid, and the cell design. It was shown by electrolysis at a controlled potential and in a galvanostatic mode that the products of methyl 5-nitro-4-oxopentanate electroreduction are hydroxyamino and amino compounds, and also ammonium chloride, nitromethane, methylhydroxylamine hydrochloride, and monomethylamine hydrochloride. Their ratio depends on the electrolysis conditions. The highest overall substance yield (61.1–66.0%) and current yield (68.1–68.6%) of 5-amino-4-oxopentanoic acid hydrochloride was achieved at a copper cathode in a filter-press cell. The content of the main substance in the electrochemically obtained samples of 5-amino-4-oxopentanoic acid was 89.5–91.0%.     

Electrochemical selective reduction of 2,4-dinitrochlorobenzene

Electrochemical behavior of 2,4-dinitrochlorobenzene was studied using the method of preparative electrolysis in an acidic medium. The effect of the cathode material, temperature, nature of the solvent, concentrations of the initial dinitro compound and hydrochloric acid on the current efficiency of chloronitroanilines and their ratio was studied. Conditions of electrosynthesis of chloronitroanilines with predominant content of 2-chloro-5-nitroaniline (72–76 %) in the reaction solutions are found providing the yield of chloronitroanilines of 83–86% and the current efficiency of about 100%.     

Electrochemical synthesis of diacetone-2-keto-L-gulonic

The electrochemical oxidation of technological-grade diacetone-L-sorbose to diacetone-2-keto-L-gulonic acid by the preparative electrolysis in alkaline media is studied. The effect of various technological parameters, namely, the cathode material, the temperature, the sodium hydroxide concentration, the current density, and the cell design, on the yield of discetone-2-keto-L-gulonic acid is considered. For the electrosynthesis of diacetone-2-keto-L-gulonic acid on the anode made of Kh18N10T stainless steel, the conditions are found that provide its total substance yield and current efficiency over all stages of oxidation and isolation from solution at the level of 88.5 and 37.5–38.0%, respectively.     

Nonanol-1 oxidation on nickel oxide electrode with the involvement of active oxygen forms

The process of nonanol-1 oxidation is studied on the nickel oxide electrode with the use of chemically bound active oxygen forms (AOF) electrochemically generated in situ from O₂, H₂O₂, and H₂O. The effect of electrolysis conditions (AOF generation schemes, current density, passed charge) on the yield of pelargonic acid is studied. The oxidation proceeds most efficiently at the current density of 5–10 mA cm^?2 as the theoretical charge is passed in the paired electrolysis mode. The current efficiency with respect to pelargonic acid is 83.7%; the substance yield is 83.8%. In addition to pelargonic acid, several oxidation side-products are found in the electrolyte. Their content increases with the increase in the charge passed as a result of further oxidation of pelargonic acid.     

Electrochemical synthesis of 1,3-dimethyl-4-amino-5-formyluracyl in the presence of ammonium chloride

The synthesis of 1,3-dimethyl-4-amino-5-formyluracyl, an intermediate of theophylline synthesis, was studied in an ammonium chloride medium using the electroreduction of 1,3-dimethyl-4-amino-5-nitrosouracyl to a diamino derivative with its further formylation. The electrolysis and formylation conditions were optimized. The reduction of 1,3-dimethyl-4-amino-5-nitrosouracyl was performed under the following conditions: its concentration was 12.0–13.5 %, the cathode was a Kh18N10T stainless steel gauze, the electrolysis was performed in the presence of ammonium chloride, the current density was 7.5–8.0 A/dm², the electrolysis temperature was 40–45°C, and the formylation temperature was 71–72°C. The substance yield of overall formylaminouracyl was 81.2–83.3% and the current efficiency was 62.0–64.5%. The developed process of 1,3-dymethyl-4-amino-5-formyluracyl synthesis was evaluated at a scaled-up laboratory setup with a filter-press cell.     

在线超声成对电合成苯甲醛和丁二酸

将间接电合成苯甲醛与电还原马来酸制备丁二酸的过程有机结合, 构建了一个新的成对电解体系, 即在隔膜电解槽中, 以纯Pb为阴极, PbO₂/Pb为阳极, 硫酸溶液为介质, 在施加超声波的条件下, 阳极氧化Ce³⁺为Ce⁴⁺, 阴极还原马来酸生成丁二酸; 同时, 在槽外采用Ce⁴⁺氧化甲苯生成苯甲醛. 实验结果表明, 阴极和阳极电解的平均电流效率分别为92.71%和87.81%, 总的电流效率高达180.52%; 且Ce⁴⁺槽外氧化甲苯为苯甲醛的收率为95.78%, 马来酸电还原为丁二酸的转化率为92.09%; 电解的槽电压与单一电解氧化Ce³⁺相比降低了0.25 V.     

Electrochemical Reduction of Arsenic Acid

It is found that arsenic acid in aqueous solutions is reduced chiefly to arsine, whose yield substantially depends on the cathode material nature and electrolysis conditions. The yield increases with the acid concentration and catholyte temperature. The maximum yield (current efficiency of about 50%) is obtained on a cadmium cathode. Hydrochloric acid or cationic surface-active substances present in the catholyte raise the arsine yield on a copper cathode by more than two times and make no impact on the yield on a cadmium cathode. A possible mechanism of the observed phenomena is discussed.     

氧阴极用于电解电渗析法制备硅溶胶研究

通过对氧阴极电解电渗析槽和析氢电解电渗析槽的槽电压、电流效率、能耗等的比较,说明在电化学法制备硅溶胶过程中,用氧阴极代替析氢电极可将电解电渗析过程返回到电渗析过程。在电流密度０～１００ｍＡ·ｃｍ－２范围内,槽电压降低０．８６～１．３Ｖ左右,可节约电能１６％左右,而其电流效率则基本上不受影响     

电化学方法固定CO2用于2-羟基-2-(4-甲氧基苯基)-丙酸甲酯的合成

在一室型电解池中, 以饱和CO₂的N,N-二甲基甲酰胺(DMF)为溶液, Mg为牺牲阳极, 不锈钢、钛、铜、镍和银为工作电极, 通过电化学方法固定CO₂, 在恒电流电解的条件下研究了对甲氧基苯乙酮的电羧化反应, 得到了重要的有机合成中间体2-羟基-2-(4-甲氧基苯基)-丙酸甲酯. 电羧化产率受支持电解质种类、电极材料、电流密度、电解电量和反应温度等影响. 经过反应条件的优化, 目标产物在恒定电流密度为5.0 mA/cm²的条件下产率达到63%. 同时, 以玻碳电极-Pt丝螺旋电极-Ag/AgI/I^-为三电极体系, 研究了对甲氧基苯乙酮的电化学行为, 根据底物在通入CO₂前后循环伏安图的变化推测了对甲氧基苯乙酮的电羧化反应机理.     

阴极冷却反应器电合成乙醛酸

以过饱和草酸水深液为阴极液 ,盐酸溶液为阳极液 ,在阴极冷却电化学反应器内草酸电解合成乙醛酸 .考察了电极温度、电解液温度、电流密度和电极材料对合成乙醛酸的时空产率和电流效率的影响 .结果表明 ,阴极冷却反应器既节省能耗 ,又可使电解过程在较高草酸浓度下进行 ,提高电流效率和时空产率 .用石墨板做阳极 ,铅做阴极 ,电流密度为 4 0 9.4 6A·m-2 ,阴极液流速 μ=1 .0 8m·s-1,电解温度为 2 0℃左右时 ,电解 3 .70h ,可得到质量分数为 3 .52 %的乙醛酸溶液 ,平均时空产率为 0 .0 3 2kg·dm-3·h     

Efficient Electrocarboxylation of p-Methylpropiophenone in the Presence of Carbon Dioxide

In the one compartment electrochemical cell 2‐hydroxy‐2‐p‐tolyl‐butyric acid methyl ester was electrosynthesized by electrochemical carboxylation of p‐methylpropiophenone in the presence of carbon dioxide. Under galvanostatic conditions, the electrocarboxylation was influenced by supporting electrolytes, cathode materials, the current density, passed charge and temperatures. Application scope of the eletrocarboxylation system was then examined, and an excellent yield of 97% was obtained when the electrolysis was carried out in DMF‐0.1 mol·L^?1 TEABr solution using cheap and environmentally benign nickel as the cathode under a controlled current density of 5.0 mA·cm^?2 until 2.8 F·mol^?1 charge passed through the cell at ?10°C. The electrochemical behavior of p‐methoxylacetophenone has been studied on the glassy carbon electrode by cyclic voltammetry and the probable mechanism was proposed accordingly.     

Spectrophotometric determination of zirconium in steels with xylenol orange

Zirconium (0.005–0.25%) is determined after acid dissolution of the steel, and fusion of insoluble matter with sodium carbonate and sodium hydrogensulphate. Niobium and other interfering ions are removed by mercury cathode electrolysis. Residual small amounts of iron(III) are masked with ascorbic acid.     

Synthesis and photolysis studies of carboxylic esters of 2-hydroxy-1,2,2-triphenylethanone: a novel tandem photocyclisation

Carboxylic esters of 2-hydroxy-1,2,2-triphenylethanone can be prepared in good yield by reaction between 2-chloro-1,2,2-triphenylethanone and a carboxylic acid in the presence of silver carbonate and silver tetrafluoroborate. Irradiation of the ester with a medium pressure mercury lamp results in a rapid and quantitative photolysis to afford the carboxylic acid and benzo[b]phenanthro[9,10-d]furan.     

利用离子膜电解法改进过硫酸铵生产研究

国内工厂生产过硫酸铵大多采用工艺简单且产品纯度高的电解法,但是电解法在生产过程中存在能耗过高的问题。这一问题限制了过硫酸铵在许多领域的进一步发展。针对这一现象,对硫酸铵电解生成过硫酸铵的设备及工艺进行设计和研究,以期达到降低能耗的目的。实验基于零极距和离子交换膜电解槽的设计,研究了加酸量、抑制剂用量、出入口温度和电解液浓度等因素对电解效率的影响。结果表明,在电解液中加酸并且在阳极液中添加抑制剂对提高电流效率和降低槽电压具有很大的影响,在最优条件下电流效率可达到98%,生产过程能耗显著降低。另外,电解槽还具有连续性生产、占地面积小的优势,进一步解决了厂家所面临的生产成本过高的问题。     

电羧化苯乙烯基苯基酮合成2,4-二苯基-4-丁酮酸

研究了常压下以CO2和苯乙烯基苯基酮为原料的电羧化反应. 在一室型电解池中, 用Mg作为辅助电极, 不锈钢、铜、镍、钛、石墨电极等作为工作电极, Ag/AgI为参比电极, 恒电位电解苯乙烯基苯基酮和CO2可得到产物2,4-二苯基-4-丁酮酸. 为提高电解产率, 优化了电解条件, 对影响该反应的溶剂、支持盐、阴极材料、电解电位、底物浓度和温度等因素作了进一步讨论. 实验结果表明, 不同的电解条件下, 苯乙烯基苯基酮的还原性能存在较大差异. 通过变化规律的研究, 找到了各个影响因素的最佳条件为: 反应温度为0 ℃, MeCN作为溶剂, 0.1 mol•L－1 四乙基四氟硼酸铵为支持盐, 不锈钢电极为工作电极, Mg棒为辅助电极, 电解电位是－1.75 V. 在此条件下恒电位电解, 2,4-二苯基-4-丁酮酸的产率可达88%. 在乙腈中还研究了苯乙烯基苯基酮的电化学行为, 推测其电羧化反应经历一个电子传递反应-化学反应-电子传递反应-化学反应(ECEC)过程.     

固定床反应器电合成乙醛酸的研究

以过饱和草酸水溶液为阴极液 ,盐酸为阳极液 ,在固定床电解槽中草酸电还原得到乙醛酸 .考察改变固定床的结构、电解温度及电流密度对生成乙醛酸电流效率和产率的影响 .结果表明 ,以铅粒作阴极 ,石墨板作阳极 ,电流密度 96 .3A·m- 2 ,阴极液空速 0 .5 0 5m·s- 1,电解温度 32℃时 ,在固定床双阳极室内反应 4 5min ,乙醛酸的电流效率仍达到 6 6 .2 % ,浓度 2 .0 2 %     

Transformations of polymers and copolymers of acrylonitrile during heterogeneous saponification

The kinetic and thermodynamic specific features of the process of heterogeneous alkaline saponification of the copolymer of acrylonitrile (92.2%), methyl acrylate (6.3%), and sodium monoithaconate (1.5%) were investigated. Chemical and infrared spectroscopic methods reveal that the saponification of the nitrile groups of copolymer of acrylonitrile proceeds faster to yield amide groups and then slower to yield carboxylate groups. The order of both stages of the process with respect to the accumulation of the respective groups was evaluated. The dependence of the rate of saponification on the packing density of the structural units was demonstrated. With increasing conversion, the fiber structure becomes looser, as demonstrated by density and sorption investigations. If acrylonitrile copolymer is treated with alkali, the carboxylate groups in the polymer substrate accumulate as a result of saponification of the ester groups of the copolymer, while the nitrile groups are predominantly transformed into the amide groups. If the degree of conversion (with respect to the CN groups) is higher than 62.7%, the copolymer abruptly suffers a marked change in its mechanical properties and gradually dissolves. The products of partial saponification of copolymer were investigated by thermomechanical methods and DTA. The polycyclization of the polymer substrate was found to proceed at a temperatures which decreases as the content of the amide groups increases.     

NaCl-KCl-CeCl3熔盐体系电解精炼铈的研究

用Ce作为模拟金属,开展了NaCl-KCl-CeCl3熔盐体系电解精炼提纯金属Ce的研究,为乏燃料干法后处理提纯U, Pu等金属提供了研究基础。研究了CeCl3浓度、电解温度和阴极电流密度对电解精炼Ce的收率和电流效率的影响,得到优化的工艺条件为:CeCl3浓度为20%~25%,电解精炼温度为900~950℃,阴极电流密度为0.35~0.45 A·cm^-2,得到了成型致密的金属铈锭,产品的收率大于70%。杂质元素Al, Fe, Cu, Cr,Mn的含量均有大幅度的下降,尤其是Fe的去除效果明显从1300×10^-6降低为200×10^-6。     

A novel photoaddition of 2-phenylbenzimidazole

Irradiation of 2-phenylbenzimidazole ( 3 ) in the presence of methyl acrylate (20 equivalents) using a medium pressure mercury lamp gives methyl 2-(2-phenylbenzimidazol-1-yl)propionate ( 4 ) (75%) whose structure has been confirmed by an X-ray analysis. A similar reaction using acrylonitrile gave only a low yield (1%) of the corresponding propionitrile derivative 5 . A mechanism involving photoexcitation of 2-phenylbenzimidazole ( 3 ) followed by sequential single electron transfer, proton transfer and radical coupling is proposed to account for the formation of the novel photoadducts 4 and 5 .     

电化学氧化苯酚合成对苯醌的研究

在H型阳离子交换膜电解槽中,以H₂SO₄电解质、阳极和阴极铅电极,研究苯酚电解氧化合成对苯醌. 讨论电流密度、电解质浓度、电解液中对苯醌浓度和萃取剂等电解条件对对苯醌收率和电流效率的影响. 经优选工艺条件为：电流密度4 A·dm^-2,H₂SO₄电解质浓度1 mol·L^-1,氯仿萃取剂. 通入3.2 Ah电量,对苯醌收率可达68%,电流效率为24.7%. 而在萃取剂存在下,对苯醌收率可提高至73%,电流效率为26%. 实验结果表明氯仿萃取剂可循环套用.