potassium dithizonate | 1234510-08-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: potassium dithizonate
• 英文别名: potassium;N'-anilino-N-phenyliminocarbamimidothioate
• CAS: 1234510-08-7
• 化学式: C₁₃H₁₁N₄S*K
• 分子量: 294.421
• InChiKey: HNEGSQYYEXPTCY-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  50.1
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  potassium dithizonate 在 盐酸 作用下， 以 水 为溶剂， 生成 双硫腙
  参考文献：
  名称：

  Synthesis and Kinetics of Sterically Altered Photochromic Dithizonatomercury Complexes

  摘要：

  Following a previous study where 12 electronically altered dithizones were synthesized, here we report on attempts to synthesize 26 dithizones. The purpose was to explore the boundaries within which dithizones may be synthesized, explore spectral tuning possibilities, and investigate steric effects on the photochromic reaction of its mercury complexes. Contrary to expectation, large substituents like phenoxy groups increased the rate of the photochromic back-reaction. In the series H-, 2-CH3-, 4-CH3-, 3,4-(CH3)(2-), 2-OC6H5-, and 4-OC6H5-dithizonatophenylmercury(II), the lowest rate of 0.0004 s(1) was measured for the 2-CH3 complex, while the rate for the 2-OC6H5 derivative was 20 times higher. A solvent study revealed a direct relationship between dipole moment and the rate of the back-reaction, while the relationship between temperature and rate is exponential, with t(1/2) = 2 min 8 s for the 4-phenoxy complex. The crystal structures of two dithizone precursors, 2-phenoxy- and 4-phenoxynitroformazan, are reported.

  DOI：

  10.1021/jp5076324
• 作为产物：
  描述：

  二苯基硫代卡巴肼 在 potassium hydroxide 作用下， 以 甲醇 为溶剂， 生成 potassium dithizonate
  参考文献：
  名称：

  Synthesis and Kinetics of Sterically Altered Photochromic Dithizonatomercury Complexes

  摘要：

  Following a previous study where 12 electronically altered dithizones were synthesized, here we report on attempts to synthesize 26 dithizones. The purpose was to explore the boundaries within which dithizones may be synthesized, explore spectral tuning possibilities, and investigate steric effects on the photochromic reaction of its mercury complexes. Contrary to expectation, large substituents like phenoxy groups increased the rate of the photochromic back-reaction. In the series H-, 2-CH3-, 4-CH3-, 3,4-(CH3)(2-), 2-OC6H5-, and 4-OC6H5-dithizonatophenylmercury(II), the lowest rate of 0.0004 s(1) was measured for the 2-CH3 complex, while the rate for the 2-OC6H5 derivative was 20 times higher. A solvent study revealed a direct relationship between dipole moment and the rate of the back-reaction, while the relationship between temperature and rate is exponential, with t(1/2) = 2 min 8 s for the 4-phenoxy complex. The crystal structures of two dithizone precursors, 2-phenoxy- and 4-phenoxynitroformazan, are reported.

  DOI：

  10.1021/jp5076324

文献信息

• Synthesis, DFT and kinetic studies of chromic S-methyldithizone
  作者：F.M.A. Muller、J. Conradie、K.G. von Eschwege

  DOI：10.1016/j.poly.2020.114386

  日期：2020.3

  Dithizone is one of the most well-known trace-metal analysis reagents, however, its S-alkylated derivatives received very little attention up to date. Synthesis, kinetic studies of its photo- and chronochromic reactions, as well as DFT and TDDFT results are presented here. For comparitive purposes the corresponding phenylmercury complex was also synthesized and included in this study. Blue-shifts in lambda(max) of the S-methylated compounds are in excess of 60 nm as compared to the metal complex. Relative geometry optimized energies, atomic charge distribution in conjunction with H-1 NMR, as well as TDDFTs all point to the pink syn geometry of S-methyldithizone as the prevalent isomer, with the yellow anti geometry only of slightly higher (3.8 kJ/mol) energy. B3LYP provides significantly better UV-visible spectrum approximation than LC-BLYP, OLYP and PW91. At 20 degrees C the rate of the chronochromic reaction is 0.0073 s(-1) in chloroform, and that of the photochromic return reaction is 0.0023 s(-1) in ethanol. (C) 2020 Elsevier Ltd. All rights reserved.
• Chemical and electrochemical oxidation and reduction of dithizone
  作者：Karel G. von Eschwege、Jannie C. Swarts

  DOI：10.1016/j.poly.2010.02.009

  日期：2010.5

  A non-aqueous electrochemical study of dithizone, H(2)Dz, 1, is compared with the chemical oxidation and reduction profile of this versatile ligand. Chemical oxidation of 1 by 12 initially leads to an isolatable disulfide-bridged species, (HDz)(2), 2(2), but ultimately monomeric dehydrodithizone. Dz, 3, is formed. Electrochemically, in CH2Cl2/0.1 mol dm(-3) [N(Bu-n)(4)][B(C6F5)(4)], two oxidation processes are observed for 1. Evidence of the electrochemical formation of the dimer 2(2) was found, but on a CV timescale the fully oxidized species, 2(2) (oxidized), did not convert to the chemically stable species 3. Regeneration of 1 during an irreversible electrochemical reduction of the electrochemically generated fully oxidized species, 2(2) (oxidized), was detected. Two further one-electron electrochemical irreversible reduction steps were also identified to ultimately generate H3Dz-, 8, one of the synthetic precursors to 1. In contrast, resolution and identification of the electron transfer steps of 1 in both dimethylsulfoxide, DMSO, or in CH2Cl2/0.1 mol dm(-3) [N('' Bu)(4)][PF6] were hampered by solvation and ion paring of [PF6](-) especially with the oxidized species of 1. A metathesis of water-soluble potassium dithizonate, KHDz, 4b, led to lipophilic [N(Bu-n)(4)][HDz], 4c. (C) 2010 Elsevier Ltd. All rights reserved.