Investigation of the electro-oxidation and oxidation of catechol in the presence of sulfanilic acid

The electrochemical oxidation of catechol (1) in the presence of sulfanilic acid (2) was investigated. Some electrochemical (EC) techniques such as cyclic voltammetry and controlledpotential coulometry were used. The oxidation reaction of catechol (1) with periodate in the presence of sulfanilic acid (2) was also investigated spectrophotometrically. The results indicate that the o-quinone derived from catechol participate in Michael addition reaction with sulfanilic acid (2). In addition, according to the ECE mechanism, the observed homogeneous rate constant (k _obs) for the reaction ofo-quinone derived from catechol (1) with sulfanilic acid (2) has been estimated by digital simulation of cyclic voltammograms.     

循环伏安法研究金属铅在硫酸溶液中形成PbO~2的过程

测取了硫酸浓度为0.5～5.1mol.dm^-^3、扫描速度为1～70mV/s的铅的循环伏安曲线.得到两个PbO~2形成峰I和II,相应地假设为PbO和PbSO~4的氧化.在较低的扫描速度下以及稀硫酸溶液中,峰值电位ψpI与扫描速度S几乎无关,峰值电流ipI近似地与(S)^1/2呈直线关系,并与PbSO~4在硫酸溶液中的溶解度相应,所以过程可能受Pb^2+离子在表面膜孔隙内的扩散所控制.在较高的扫描速度下,δψpi/δlogS=50mV,属于不可逆过程,对于峰II PbSO~4的氧化过程也进行了初步讨论.     

2,2'-联吡啶类催化铬酸氧化异丙醇的动力学研究

2,2'-联吡啶类和它的相关化合物催化铬酸氧化异丙醇非常有效. 当2,2'-联吡啶分子的4- 和4'- 位连有甲基或甲氧基等供电基时, 催化活性加强; 当4- 和4'- 位连有吸电基氯原子时, 催化活性削弱. 2,2'-联吡啶类, Cr(Ⅵ)和异丙醇的三分子螯合物分解为产物的一步为限速步骤.     

Pt电极上乙醛吸附及氧化的现场FTIR反射吸收光谱电化学研究

本文用现场FTIR反射吸收光谱法和循环伏安法研究了Pt电极上HCl, H2SO4水溶液中乙醛的吸附及氧化过程。实验结果表明, 0.3至1.0V(vs. SCE)电势范围内乙醛主要以式I吸附于电极表面上, 并发生了生成乙酸的电化学反应, 产物乙酸可能以式II吸附。对于H2SO4水溶液中, 上述电势范围内电极表面上还检测出硫酸根离子与乙醛和乙酸的竞争吸附。     

水对胆绿素在二甲基甲酰胺中电化学氧化反应的影响

本文采用现场时间分辨光谱电化学技术结合循环伏安电化学方法对胆绿素(BV)在纯二甲基甲酰胺(DMF)和DMF-H~2O混合溶剂中的电化学氧化反应进行了较为系统的研究, 并提出了相应的反应机理。实验中发现, 在有机溶剂DMF中引入水不但促进了BV氧化反应的进行, 而且还使BV的氧化反应由在DMF中的ECEC历程转变为ECCECC反应过程。     

金属氧化物微粒修饰电极对儿茶酚和对苯二酚的电催化

本文研究儿茶酚和对苯二酚在金属氧化物微粒修饰电极上的电化学行为,与抗坏血酸和草酸不同,不仅儿茶酚和对二酚的氧化反应发生了电催化,而且它们的还原反应也发生了电催化,用薄层电池循环伏安法研究了儿茶酚和对苯二酚在此修饰电极表面的吸附,并探讨了电催化反应机理。证明了儿茶酚和对苯二酚在MOx/GC电极上的吸附,是发生电催化的主要原因,儿茶酚、对苯二酚和抗坏血酸的混合物在金属氧化物微粒修饰电极上的波峰明显分开,有可能同时测定儿茶酚和抗环血酸,提供了分析应用的可能性。     

维生素C氧化反应的研究: H2O2-Cu^2^+-磷酸体系中的反应动力学

研究了在铜离子存在时的弱酸性条件下, 用过氧化氢氧化维生素C, 并用直接分光光度法测定未变化的酸, 表明维生素C的催化氧化是以链式反应机制进行的.     

铌(V)-酒石酸-2-(5'-溴-2'-吡啶偶氮)-5-二乙氨基苯酚三元配便物的汞电极上的吸附

本文用线性变势吸附伏安法研究了铌(V)-酒石酸-2-(5'-溴-2'-吡啶偶氮)-5-二乙氨基苯酚三元配合物在汞电极上的电吸附性质, 测定了表面浓度, 讨论了吸附浓度的表达式及其与吸附时间、金属离子浓度、配位体浓度的关系, 验证了吸附量与电极面积及还原峰电流的关系。证明了配合物在电极上的还原是一个可逆吸附的还原过程。     

Kinetic and mechanistic studies on the oxidation of sulfanilic acid by peroxomonophosphoric acid

Oxidation of sulfanilic acid to the corresponding azoxy derivative by peroxomonophosphoric acid (PMPA) has been studied in aqueous medium. The observed bell-shaped pH-rate profile has been rationalized on the basis of protonation of the amino group and ionization into different PMPA species and a suitable rate law has been proposed. The mechanism of oxidation involves the nucleophilic attack of nitrogen on the electrophilic peroxo oxygen.

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- (PMPA) . pH— , PMPA . .

     

Electrochemical oxidation of catechol in the presence of cyclopentadiene. Investigation of electrochemically induced Diels-Alder reactions

We describe the synthesis and kinetic evaluation of compounds from [4 + 2] alone and [4 + 2] followed by [2 + 2] cycloaddition reactions of electrochemically generated o-benzoquinone with 1,3-cyclopentadiene.     

次溴酸异莰烷酯的光分解反应及其在Nojj菊醇合成中的应用

本文研究了异莰烷醇两种异构体在Br2-HgO光照条件下的Barton反应, 得到环醚,产率较高。由环醚开环经五步转化选择性地合成了Noji菊醇(Nojigiku alcohol); 环醚可作为β-檀香醇合成中的潜在中间体。     

过氧化氢水溶液催化氧化环戊烯制备戊二醛

用过氧化氢水溶液氧化环戊烯制得戊二醛。对多种催化剂-溶剂体系进行了试验, 在钨酸-叔丁醇体系中得到了最高的戊二醛得率: 近60%(30%过氧化氢水溶液为氧化剂)或80%(50%过氧化氢水溶液为氧化剂)。同时, 对该反应的机理进行了初步研究, 提出环戊烯被过氧化氢氧化为戊二醛是经过环氧化物中间产物的观点。     

铅锑合金在硫酸溶液中的阳极膜II.电位对阳极膜生长的影响

本文使用线性电位扫描法还原预恒电位法氧化形成的阳极膜,研究电位对Pb-7Sb,Pb-7Sb-0.3Ag和Pb-5Sb-0.2As三种合金在30℃,4.5MH2SO4溶液中的阳极膜的生长速度的影响,在铅锑合金中添加银可降低合金阳极膜的生长速度,但在高电位1.4V(vs.Hg2SO4电极时,Pb-7Sb-0.3Ag合金上的PbO2膜的生长速度在上述三合金中居首,这可能是由于在银上的氧析出超电势较低的缘故,本文讨论了这种阳极膜的生长机理。     

Kinetics and mechanism of oxidation of sulfanilic acid by periodate ion in aqueous medium

Results of kinetic studies of the sodium metaperiodate oxidation of sulfanilic acid in aqueous medium are discussed. A mechanism for the formation of azobenzene-4,4-disulfonic acid, isolated and characterized as its S-benzylisothiuronium derivative, is proposed.

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. -4,4- , S- .

     

13β-乙基-3-甲氧基-甾-1,3,5(10),9(11)-四烯-17β-醇的间氯过氧苯甲酸氧化反应

研究了13β-乙基-3-甲氧基-甾-1,3,5(10),9(11)-四烯-17β-醇与间氯过氧苯甲酸的氧化反应, 得到了9β-羟基-11酮化合物和一个未知化合物9α-过氧甲氧基-11-酮化合物。推测了反应机理, 讨论了未知物的化学结构和构型。     

Cu(II)氧化抗坏血酸的动力学和机理

本文在总离子强度I=1.00mol.dm^-^3、[Cu^2^+]>>[H2A]、[H^+]>>[H2A]、无氧及无缓冲剂存在的条件下, 研究Cu(II)氧化抗坏血酸(H2A)的动力学和机理. 发现Cu(II)与H2A不发生配位反应, 但以Cl^-存在的情况下, 确有Cu(II)的H2A配合物生成, Cu(II)氧化H2A反应的速率方程为r={a+b[Cl^-]}[Cu^2^+]{[H+]+Ka}^-^2, 25℃时a和b值分别为4.08×10^-^4s^-^1和0.555dm^3.s^-^1.mol^-^1. Cu(II)氧化H2A反应的表观活化能为68.1KJ.mol^-^1. 根据动力学结果, 提出了反应机理, 并给出了配合物ClCuHA的结构形式.     

沸石分子筛孔道中聚苯胺的选择性掺杂研究

用电化学方法聚合分子筛孔道内的苯胺, 根据聚苯胺在无机质子酸中的掺杂反应研究了ZSM-5,Y型分子筛对磷钼杂多酸的形状选择作用     

Electrochemical oxidation of catechol in the presence of 2-thiouracil: application to electro-organic synthesis

The electrochemical oxidation of catechol in the presence of 2-thiouracil (as a nucleophile) has been studied in aqueous solutions using cyclic voltammetry and controlled-potential coulometric techniques. The results indicate that catechol participating in a 1,4 (Michael) addition reaction converts to a new thiadiazafluorenone compound. The electrochemical synthesis of this compound has been successfully performed in an undivided cell in a good yield and purity and was characterized by IR, ¹H and ¹³C NMR, mass spectrometry and elemental analysis.     

Kinetic, mechanistic and spectral studies for the oxidation of sulfanilic acid by alkaline hexacyanoferrate(III)

The kinetics of oxidation of sulfanilic acid (p-aminobenzenesulfonic acid) by hexacyanoferrate(III) in alkaline medium was studied spectrophotometrically. The reaction showed first order kinetics in hexacyanoferrate(III) and alkali concentrations and an order of less than unity in sulfanilic acid concentration (SAA). The rate of reaction increases with increase in alkali concentration. Increasing ionic strength increases the rate but the dielectric constant of the medium has no significant effect on the rate of the reaction. A retarding effect was observed by one of the products i.e. hexacyanoferrate(II) (HCF(II)). A mechanism involving the formation of a complex between sulfanilic acid and hexacyanoferrate(III) has been proposed. The reaction constants involved in the mechanism are evaluated. There is a good agreement between the observed and calculated rate constants under different experimental conditions. Investigations at different temperatures allowed the determination of the activation parameters with respect to the slow step of the proposed mechanism.