Wursters Rot | 33624-86-1

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: Wursters Rot
• 英文别名: 4-Imino-N,N-dimethylcyclohexa-2,5-dien-1-iminium；(4-iminocyclohexa-2,5-dien-1-ylidene)-dimethylazanium
• CAS: 33624-86-1
• 化学式: C₈H₁₁N₂
• 分子量: 135.189
• InChiKey: YXBRSYBKYPDUME-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  26.9
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Wursters Rot 在 hexacyanoferrate(II) 作用下， 以 水 为溶剂， 生成 N,N-dimethyl-p-phenylenediamine radical cation
  参考文献：
  名称：

  Nickel, Ulrich; Jaenicke, Walther, Berichte der Bunsen-Gesellschaft, 1982, vol. 86, # 8, p. 695 - 701

  摘要：

  DOI：
• 作为产物：
  描述：

  4-dimethylaminophenylamine dihydrochloride 在 碘 作用下， 以 水 为溶剂， 生成 Wursters Rot
  参考文献：
  名称：

  An Investigation of Electron Transfer Reactions between Aromatic and Quinoid Systems

  摘要：

  AbstractA classical organic redox reaction is the conversion of an aromatic compound from its reduced form R to a semioxidized state S, and further to a totally oxidized (quinoid) species T. Complex redox systems are present in a reaction of quinoid and aromatic forms derived from different parent compounds. In this case, the exchange of one or two electrons in one step between T and R can be distinguished experimentally. These reactions were investigated in a stopped‐flow apparatus with optical detection. In the system N,N,N′,N′‐tetramethyl‐para‐phenylene‐diamine/N,N‐dimethyl‐para‐phenylene‐diamine the rate constants for all elementary reactions have been determined. Protonated, and unprotonated R were found to be reactive. In this system, as well as the others considered, no direct transfer of two electrons between T1 and R2 takes place. The essential steps of the mechanism have to be seen in a mixed symproportionation yielding S1 and S2, and a subsequent fast oxidation of S2 by surplus starting material T1. As a generalization, a tangent criterion has been derived to distinguish between one‐ and two‐electron steps in such mixed redox systems.

  DOI：

  10.1002/bbpc.198800110

文献信息

• Activation parameters and mechanism of the deamination of N-substituted quinone monoimines and di-imines
  作者：Ulrich Nickel、Walther Jaenicke

  DOI：10.1039/p29800001601

  日期：——

  activation are strongly negative for k′ and strongly positive for k″. The activation parameters of the acid and alkaline deamination of N-substituted quinone di-imines were also measured. With regard to the activation entropies similar results were found as for the quinone monoimines. For all deaminations a common mechanism with a preceding solvation equilibrium is proposed.

  使用紫外光谱，通过停止流方法在278至323 K之间的温度，pH在1至9的pH范围内，通过水溶液测量了六个N-取代的醌单亚胺的脱氨速率。观测到的速率常数由k = k '[H 2 O] + k ” [OH – ]给出；ķ '和ķ “由12个数量级不同。k ′和k ′的激活焓几乎相等。活化的熵是强负对ķ '和强阳性ķ “。酸和碱脱氨的活化参数还测量了N-取代的醌二亚胺。关于活化熵，发现与醌单亚胺相似的结果。对于所有脱氨基，提出了具有预先溶剂化平衡的通用机理。
• Scanning electrochemical microscopy Kinetics of chemical reactions following electron-transfer measured with the substrate-generation–tip-collection mode
  作者：Rachel D. Martin、Patrick. R. Unwin

  DOI：10.1039/a707984b

  日期：——

  The substrate-generation–tip-collection (SG–TC) mode of the scanning electrochemical microscope (SECM) is used as a new approach to investigate the kinetics of EC processes. Under the conditions of interest, a species O is generated at a macroscopic substrate (generator) electrode, with potential-step control, through the diffusion-limited electrolysis of a solution species R (E step). As O diffuses away from the generator, it undergoes a first order chemical reaction in solution (C step). A fraction of O is collected by electrolysis back to R at an externally biased ultramicroelectrode (UME), positioned directly over the substrate. This promotes the diffusional feedback of R to the substrate. Theory for the problem, relating the time-dependent tip current response to the rate constant for the C step and the tip–substrate electrode separation is developed numerically. Results of the calculations illustrate how the characteristic features of the tip current transients: peak current, peak time and post-half-peak time, depend on the kinetics of the C step and the inter-electrode separation. It is shown that both the kinetics and tip–substrate separation can be determined independently from a single transient by simply measuring the peak current and peak time. The theoretical results are validated experimentally through model studies of the oxidative deamination of N,N,-dimethyl-p-phenylenediamine (DMPPD) in aqueous solution at high pH. The effective second-order rate constant for the deamination step is in excellent agreement with values measured by alternative methods.

  扫描电化学显微镜 (SECM) 的底物生成 - 尖端收集 (SG - TC) 模式被用作研究 EC 过程动力学的新方法。在感兴趣的条件下，通过溶液物质 R 的扩散限制电解（E 步骤），在电位阶跃控制下，在宏观基板（发生器）电极处生成物质 O。当 O 扩散离开发生器时，它在溶液中发生一级化学反应（C 步骤）。通过直接位于基板上方的外部偏置超微电极 (UME) 电解，将一小部分 O 收集回 R。这促进了 R 向基底的扩散反馈。该问题的理论，将时间相关的尖端电流响应与 C 步骤的速率常数和尖端与基底电极分离联系起来，以数值方式发展。计算结果说明了尖端电流瞬变的特征：峰值电流、峰值时间和半峰值后时间如何取决于 C 阶跃和电极间分离的动力学。结果表明，通过简单地测量峰值电流和峰值时间，可以独立于单个瞬态来确定动力学和尖端与基底的分离。通过 N,N,-二甲基对苯二胺 (DMPD) 在高 pH 水溶液中氧化脱氨的模型研究，对理论结果进行了实验验证。脱氨步骤的有效二阶速率常数与替代方法测量的值非常一致。
• Electrochemical study of the heterogeneously catalysed reaction between N,N-dimethyl-p-phenylenediamine and CoIII(NH3)5Cl2+ at monometallic and bimetallic surfaces of silver and gold
  作者：Yao-Hong Chen、Ulrich Nickel、Michael Spiro

  DOI：10.1039/ft9949000617

  日期：——

  The mechanism of the heterogeneously catalysed reaction between N,N-dimethyl-p-phenylenediamine and CoIII(NH3)5CI2+ at silver, gold and silver-on-gold (Ag/Au) discs has been studied by means of electrochemical methods. Both the mixed (or mixture) potentials and the mixture currents were determined by recording the current–potential curves of the reactants. Silver halide, formed during the reaction, was determined by subsequent galvanostatic reduction. The reaction at silver was strongly inhibited by the formation of silver halide whereas the reaction at gold was inhibited by adsorption of the organic compounds as well as by iodide. At Ag/Au discs almost no inhibition occurred. The explanation is that the reduction of the cobalt complex takes place predominantly at the silver surface whereas the simultaneous oxidation of the p-phenylenediamine occurs on the gold. In this way the formation of inhibiting silver halide is suppressed as well as the inhibition caused by the adsorption of p-phenylenediamine.

  通过电化学方法研究了 N,N-二甲基对苯二胺与 CoIII(NH3)5CI2+ 在银、金和银-金（Ag/Au）圆盘上发生异相催化反应的机理。通过记录反应物的电流-电位曲线，确定了混合（或混合物）电位和混合物电流。反应过程中形成的卤化银是通过随后的电静电还原测定的。银的反应受到卤化银形成的强烈抑制，而金的反应则受到有机化合物吸附和碘化物的抑制。在银/金圆盘上几乎没有抑制作用。原因是钴络合物的还原主要发生在银表面，而对苯二胺的氧化同时发生在金表面。这样，抑制性卤化银的形成以及对苯二胺的吸附所引起的抑制作用就被抑制了。
• Mechanism and Kinetics of the Photocatalyzed Oxidation of p-Phenylenediamines by Peroxydisulfate in the Presence of Tri-2,2'-bipyridylylruthenium(II)
  作者：Ulrich Nickel、Yao-Hong Chen、Siegfried Schneider、Maria I. Silva、Hugh D. Burrows、Sebastiao J. Formosinho

  DOI：10.1021/j100062a026

  日期：1994.3

  The autocatalytic oxidation of p-phenylenediamines with peroxydisulfate can be strongly enhanced by irradiation in the presence of tri-2,2'-bipyridylylruthenium(II). Ru(bpy)3(2+) acts as photosensitizer and photocatalyst. First, Ru(bpy)33+ is formed by quenching excited Ru*(bpy)3(2+) with S2O8(2-). Then the ruthenium(III) complex oxidizes p-phenylenediamine. The resulting Ru(bpy)3(2+) can start the cycle again. The photocatalytic oxidation of N,N-diethyl-p-phenylenediamine as well as the dark reactions were studied with stopped-flow techniques. The mechanism of this complex reaction is discussed in detail.
• Nickel, U.; Ruehl, N.; Zhou, B. M., Zeitschrift fur physikalische Chemie (Neue Folge), 1986, vol. 148, p. 33 - 52
  作者：Nickel, U.、Ruehl, N.、Zhou, B. M.

  DOI：——

  日期：——