1-(2-Methoxyanilino)-3-(2-methoxyphenyl)iminothiourea

• 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-(2-Methoxyanilino)-3-(2-methoxyphenyl)iminothiourea
• 化学式: C₁₅H₁₆N₄O₂S
• 分子量: 316.384
• InChiKey: IRUYXBIBVHZVDC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  99.3
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1-(2-Methoxyanilino)-3-(2-methoxyphenyl)iminothiourea 在 sodium hydroxide 作用下， 生成 1,5-bis-(2-methoxy-phenyl)-3-methylsulfanyl-formazan
  参考文献：
  名称：

  Dubenko; Pel'kis, Zhurnal Obshchei Khimii, 1959, vol. 29, p. 435;engl.Ausg.S.437

  摘要：

  DOI：
• 作为产物：
  描述：

  N',2-bis(2-methoxyphenyl)hydrazine-1-carbothiohydrazide 在 potassium hydroxide 作用下， 以 甲醇 为溶剂， 生成 1-(2-Methoxyanilino)-3-(2-methoxyphenyl)iminothiourea
  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

• Preferential solvation and molecular orbital calculation studies of solvatochromic mesoionic 2,3-diaryl-2H-tetrazolium-5-thiolate derivatives
  作者：A. Taha、A. Mageed Kiwan

  DOI：10.1039/b008263p

  日期：——

  Solvent effects on the electronic spectra of some mesoionic 2,3-diaryl-2H-tetrazolium-5-thiolate derivatives were investigated in thirteen pure solvents and eight water–organic solvent mixtures. In pure solvents, the solvatochromic shifts of the mesoionic compounds are found to be mainly influenced by the AN, α and π* solvent parameters. The relative contributions of these parameters depend on the nature of the substituents on the phenyl moieties of the mesoionic derivatives. Thus, electron-donating substituents increase the relative contribution of both AN and α parameters but decrease the relative contribution of the π* parameter. The behavior of the mesoionic derivatives in water–organic solvent mixtures has been explained in terms of preferential solvation. Different criteria were considered to evaluate the extent of preferential solvation in different solvent mixtures, iz. the excess function (Δν), iso-solvation point (Xiso) and preferential solvation constant (K). Three distinct preferential solvation patterns for the mesoionic derivatives in different water–organic solvent mixtures were elucidated: negative deviation in water–alcohol and water–Py, positive deviation in water–Me2CO and water–DMF, and a dual behavior in water–MeCN and water–Diox solvent mixtures. Molecular orbital calculations have been carried out for the mesoionic derivatives and the data correlated with the experimental results.

  研究了溶剂在 13 种纯溶剂和 8 种水有机溶剂混合物中对一些介离子 2,3-二芳基-2H-四唑-5-硫酸酯衍生物电子光谱的影响。研究发现，在纯溶剂中，介离子化合物的溶度色移主要受 AN、α 和 π* 溶剂参数的影响。 这些参数的相对贡献取决于介离子衍生物苯基上取代基的性质。因此，电子捐赠取代基会增加 AN 和 α 参数的相对贡献，但会减少 π* 参数的相对贡献。介离子衍生物在水-有机溶剂混合物中的行为可以用优先溶解来解释。在评估不同溶剂混合物中的优先溶解度时，考虑了不同的标准，即过量函数（Δν）、等溶点（Xiso）和优先溶解常数（K）。阐明了介离子衍生物在不同水-有机溶剂混合物中的三种不同的优先溶解模式：在水-醇和水-吡中的负偏离，在水-Me2CO 和水-DMF 中的正偏离，以及在水-MeCN 和水-二氧六环溶剂混合物中的双重行为。我们对介离子衍生物进行了分子轨道计算，并将计算结果与实验结果进行了对比。
• 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.
• The Synthesis of Some Substituted Thiocarbazones¹
  作者：D. S. Tarbell、C. W. Todd、M. C. Paulson、E. G. Lindstrom、V. P. Wystrach

  DOI：10.1021/ja01184a027

  日期：1948.4