1,5-bis-(3,4-dimethyl-phenyl)-thiocarbazone | 110377-81-6

• 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: 1,5-bis-(3,4-dimethyl-phenyl)-thiocarbazone
• 英文别名: 1,5-Bis-(3,4-dimethyl-phenyl)-thiocarbazon；1-(3,4-Dimethylanilino)-3-(3,4-dimethylphenyl)iminothiourea；1-(3,4-dimethylanilino)-3-(3,4-dimethylphenyl)iminothiourea
• CAS: 110377-81-6
• 化学式: C₁₇H₂₀N₄S
• 分子量: 312.439
• InChiKey: GYLIELROQUMXHE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  80.9
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1,5-bis-(3,4-dimethyl-phenyl)-thiocarbazone 在 sodium hydroxide 作用下， 生成 1,5-bis-(3,4-dimethyl-phenyl)-3-methylsulfanyl-formazan
  参考文献：
  名称：

  Dubenko; Pelkis, Zhurnal Obshchei Khimii, 1959, vol. 29, p. 3649; engl.Ausg.S.3432

  摘要：

  DOI：
• 作为产物：
  描述：

  1,5-bis(3,4-dimethylphenyl)-3-nitroformazan 在 ammonium sulfide 、 potassium hydroxide 作用下， 以 甲醇 、 乙醇 、 水 为溶剂， 反应 0.33h， 生成 1,5-bis-(3,4-dimethyl-phenyl)-thiocarbazone
  参考文献：
  名称：

  Synthesis and kinetics of electronically altered photochromic dithizonatophenylmercury(II) complexes

  摘要：

  A series of phenyl-substituted dithizones were synthesized, and preparation of the corresponding series of photochromic phenylmercury(II) complexes is for the first time reported. Adaption of previous methods enhanced synthesis convenience and product yields. A single crystal X-ray data collection of the ortho-S-methyl nitroformazan reaction intermediate was done. ADF computed molecular orbitals of the title compound show the HOMO and LUMO orbitals stretching along the entire ligand. The spontaneous back reaction kinetics of dithizonatophenylmercury(II) was studied at varied concentrations, temperatures and in different solvents. An exponential correlation was found between the rate of reverse isomerization and temperature, while increased solvent polarity and decreased molar mass facilitate higher return rates. The kinetic study of the series of twelve electronically altered complexes yielded a lowest rate of 0.0002 s(-1) the ortho-methyl derivative, while the highest rate of 0.0106 s(-1) was measured for the meta-methoxy derivative. (C) 2012 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jphotochem.2012.11.009

文献信息

• Studies on Tetramethyldithizone Isomers and Their Reactions with Metal Ions
  作者：A. M. Kiwan、F. M. Hassan、W. Hamdan

  DOI：10.1246/bcsj.62.325

  日期：1989.1

  Six bis(dimethylphenyl) analogues of dithizone are prepared, characterized and their reactions with metal ions in a two phase system are reported. The extraction equilibria of their complexes with Cd(II), Co(II), Hg(II), Pb(II), Tl(I), Zn(II), and Bi(III) as well as their spectral characteristics are described. Complete extraction of these metal chelates requires higher pH’s than those needed for the unsubstituted dithizone. The molar absorptivities of Bi(III) complexes with bis(3,4-dimethylphenyl)-, and bis(3,5-dimethylphenyl) analogues are higher than the corresponding value of Bi(III) dithizonate. The molar absorptivities of Cu(II) and Hg(II) (in CCl4) complexes with bis(3,5-dimethylphenyl) analogue are also higher than the corresponding values of the unsubstituted dithizone complexes.

  本研究制备了六种双(二甲基苯基)二硫酮类似物，对其进行了表征，并报告了它们在双相体系中与金属离子的反应。报告描述了它们与 Cd(II)、Co(II)、Hg(II)、Pb(II)、Tl(I)、Zn(II) 和 Bi(III) 复合物的萃取平衡及其光谱特征。完全萃取这些金属螯合物所需的 pH 值要高于未取代的二硫酮所需的 pH 值。双（3,4-二甲基苯基）和双（3,5-二甲基苯基）类似物的 Bi（III）络合物的摩尔吸收率高于二硫酮 Bi（III）的相应值。铜（II）和汞（II）（在 CCl4 中）与双（3,5-二甲苯基）类似物的摩尔吸收率也高于未取代的二硫酮配合物的相应值。
• Femtosecond Laser Spectroscopy and DFT Studies of Photochromic Dithizonatomercury Complexes
  作者：Karel G. von Eschwege、Gurthwin Bosman、Jeanet Conradie、Heinrich Schwoerer

  DOI：10.1021/jp410186y

  日期：2014.2.6

  The ultrafast dynamics of the photochromic reaction of dithizonatophenylmercury(II) was recently reported. For purpose of investigating the effect of electronically different substituents (X = o-F, m-F, p-F, p-Cl, o-CH3, m-CH3, p-CH3, m,p-diCH(3), p-OCH3, o-SCH3, and p-SCH3) on this reaction, a series of phenyl-substituted dithizones were synthesized and complexed with phenylmercury(II). A variation of more than 3 ps in ground state repopulation times was observed, with the o-methyl derivative absorbing both at shortest wavelength and having the fastest repopulation time, while the p-S-methyl derivative lies at the opposite extremity. An increase in both decay times and lambda(max) values is generally reflected by an increase in electron density in the chromophore. Ultrafast rates also proved to be dependent on solvent polarity, while a profound solvatochromic effect was observed in the transition state absorbance. Density functional theory realistically simulated isomer stabilities, electronic spectra and molecular orbitals. Increased electron density enhances stability in the photoexcited blue isomer relative to the orange resting state, as seen from a comparison between orange and blue isomer total bonding energies. A linear trend between computed HOMO energies and experimental lambda(max) of related aliphatic substituted derivatives was found.
• Synthesis and kinetics of electronically altered photochromic dithizonatophenylmercury(II) complexes
  作者：Karel G. von Eschwege

  DOI：10.1016/j.jphotochem.2012.11.009

  日期：2013.1

  A series of phenyl-substituted dithizones were synthesized, and preparation of the corresponding series of photochromic phenylmercury(II) complexes is for the first time reported. Adaption of previous methods enhanced synthesis convenience and product yields. A single crystal X-ray data collection of the ortho-S-methyl nitroformazan reaction intermediate was done. ADF computed molecular orbitals of the title compound show the HOMO and LUMO orbitals stretching along the entire ligand. The spontaneous back reaction kinetics of dithizonatophenylmercury(II) was studied at varied concentrations, temperatures and in different solvents. An exponential correlation was found between the rate of reverse isomerization and temperature, while increased solvent polarity and decreased molar mass facilitate higher return rates. The kinetic study of the series of twelve electronically altered complexes yielded a lowest rate of 0.0002 s(-1) the ortho-methyl derivative, while the highest rate of 0.0106 s(-1) was measured for the meta-methoxy derivative. (C) 2012 Elsevier B.V. All rights reserved.
• Pel'kis et al., Zhurnal Obshchei Khimii, 1957, vol. 27, p. 1849,1852;engl.Ausg.S.1913,1915
  作者：Pel'kis et al.

  DOI：——

  日期：——
• Synthesis and Kinetics of Sterically Altered Photochromic Dithizonatomercury Complexes
  作者：Ernestine Alabaraoye、Karel G. von Eschwege、Nagarajan Loganathan

  DOI：10.1021/jp5076324

  日期：2014.11.20

  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.