(1Z)-N,2-di-p-tolyldiazene-1-carbohydrazonothioic acid | 16026-13-4

• 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: (1Z)-N,2-di-p-tolyldiazene-1-carbohydrazonothioic acid
• 英文别名: di(p-chlorophenyl)thiocarbazone
• CAS: 16026-13-4
• 化学式: C₁₅H₁₆N₄S
• 分子量: 284.4
• InChiKey: NOHADVDPZZDVAZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.13
• 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：

  (1Z)-N,2-di-p-tolyldiazene-1-carbohydrazonothioic acid 在 氨 、 双氧水 作用下， 以 氯仿 、 水 为溶剂， 生成 2,3-di-(p-tolyl)-2H-tetrazolium-5-thiolate
  参考文献：
  名称：

  Preferential solvation and molecular orbital calculation studies of solvatochromic mesoionic 2,3-diaryl-2H-tetrazolium-5-thiolate derivatives

  摘要：

  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。

  DOI：

  10.1039/b008263p
• 作为产物：
  描述：

  3-nitro-1,5-dip-tolylformazan 在 ammonium sulfide 、 氧气 、 potassium hydroxide 作用下， 生成 (1Z)-N,2-di-p-tolyldiazene-1-carbohydrazonothioic acid
  参考文献：
  名称：

  Femtosecond Laser Spectroscopy and DFT Studies of Photochromic Dithizonatomercury Complexes

  摘要：

  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.

  DOI：

  10.1021/jp410186y

文献信息

• 一种超声波无溶剂合成噻二唑类化合物的方 法
  申请人：河南科技大学

  公开号：CN107674042B

  公开（公告）日：2020-09-25

  本发明涉及一种超声波无溶剂合成噻二唑类化合物的方法，采用喷雾方法使液体原料与固体原料充分接触，在超声波振荡下完全反应，高效、高收率地合成出3‑取代苯基‑5‑取代苯偶氮基‑[1,3,4]‑噻二唑‑2‑硫酮类化合物，最高产物收率可达92.5%。该方法简单易行，便于操作，且无需加入任何溶剂，具有反应设备简单，速度快，易操作，无副产物，无溶剂无污染，易分离提纯等优点；具有良好的工业化应用前景。
• Preparation of o.o'-dichlorodithizone and a study of its metal complexing properties
  作者：R.S. Ramakrishna、M. Fernandopulle

  DOI：10.1016/s0003-2670(01)80358-5

  日期：——

  various metal complexes were determined. Values for wavelengths of maximum absorption and molar extinction coefficients are g'ven; the former increase in the order Ag+< Hg2+< Bi3+< Pb2+< Cd2+< Zn2+< Cu2+ and the latter in the order Ag+< Bi3+< Cu2+< Hg2+< Pb2+< Cd2+< Zn2+. Substitution of chlorine produces a regular bathochromic shift in wavelength of maximum absorption for reagent and their metal complexes

  合成了o,o'-二氯双硫腙，并在四氯化碳中测定了其光谱特性。确定了定量提取各种金属配合物的 pH 值范围。最大吸收波长和摩尔消光系数的值是 g'ven；前者按 Ag+< Hg2+< Bi3+< Pb2+< Cd2+< Zn2+< Cu2+ 的顺序增加，后者按 Ag+< Bi3+< Cu2+< Hg2+< Pb2+< Cd2+< Zn2+ 的顺序增加。与双硫腙相比，氯的取代会在试剂及其金属配合物的最大吸收波长上产生规律的红移。没有证据表明邻位取代基的“空间效应”会干扰 Zn、Cd、Hg 和 Pb 的螯合环形成；结果证实，复合物的形成是通过试剂的硫代-H 发生的。在 5-11 的 pH 值范围内研究了铅作为其邻二氯二硫腙酸盐进入四氯化碳的可萃取性，并测量了萃取常数。
• Synthesis of 2,3-Diaryltetrazole-5-thiones and Theoretical Studies on Atomic Charge Distributions of 2,3-Diphenyltetrazole-5-thione
  作者：Fangfang Jian、Pusu Zhao、Lan Zhang、Yuxia Hou

  DOI：10.1021/jo0504767

  日期：2005.10.1

  Four 2,3-diaryltetrazole-5-thiones have been synthesized in high yields using a new synthetic method under mild reaction conditions. Theoretical calculations of the structure, vibrational frequencies, and natural population analysis (NPA) of atomic charge distributions on 2,3-diphenyltetrazole-5-thione 1 have been performed by DFT-B3LYP, HF, and MP2 methods using several basis sets. According to the

  使用新的合成方法，在温和的反应条件下，高收率合成了四种2,3-二芳基四唑-5-硫酮。已经通过DFT-B3LYP，HF和MP2方法使用几个基础集对结构，振动频率和2,3-二苯基四唑-5-硫酮1上的原子电荷分布进行自然人口分析（NPA）的理论计算。根据NPA结果，已经提出了一种新的共振杂化结构1，其具有环外硫原子和带有负电荷的四唑环和带有正电荷的两个苯环。在这种新的提议结构的基础上，计算结果可以从逻辑上解释实验事实。此外，新化学性质为1 已经预测：质子化不仅应发生在环外的S原子上，而且应发生在具有负电荷的N个原子上。
• 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.
• 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.