O-(2,6-diphenyl)phenyl N,N-dimethylthiocarbamate | 16241-18-2

• 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: O-(2,6-diphenyl)phenyl N,N-dimethylthiocarbamate
• 英文别名: O-(2,6-diphenylphenyl)dimethylcarbamothioate；O-(2,6-diphenyl)phenyl N,N-dimethylthiolcarbamate；O-<(2.6-Diphenyl)-phenyl>-dimethylthiocarbaminat；O-(2,6-diphenylphenyl) N,N-dimethylcarbamothioate
• CAS: 16241-18-2
• 化学式: C₂₁H₁₉NOS
• 分子量: 333.454
• InChiKey: APRLOMXDPXKXFZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  44.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  O-(2,6-diphenyl)phenyl N,N-dimethylthiocarbamate 以 N-甲基吡咯烷酮 为溶剂， 反应 3.0h， 以64%的产率得到S-(2,6-diphenyl)phenyl N,N-dimethylthiocarbamate
  参考文献：
  名称：

  2,6-二芳基硫酚中的全空间极性π相互作用。

  摘要：

  极性基团与芳香族分子之间的分子识别对于合理的药物设计至关重要。尽管已经公认许多极性官能团通过能量上有利的极性π相互作用与富电子芳族残基相互作用，但对硫醇与芳族体系之间的联系了解甚少。在这里，我们报告了对具有中心硫酚环和两个侧链芳环的2,6-二芳基硫酚进行的物理有机化学研究，这些芳环的电子性质可调节，是由远处对位取代基引起的。哈米特分析显示p K a值和质子亲和力与取代基的哈米特西格玛（Hammett sigma）值密切相关。附加的能量分解分析支持以下结论：贯穿空间的SH-π相互作用和S -- π相互作用均有助于2,6-二芳基硫酚的分子内稳定。

  DOI：

  10.1002/cphc.202000132
• 作为产物：
  描述：

  苯硼酸 在 四(三苯基膦)钯 、 sodium hydride 、 sodium carbonate 、 sodium hydroxide 作用下， 以 四氢呋喃 、 N-甲基吡咯烷酮 、 甲醇 、 水 、 甲苯 为溶剂， 反应 74.25h， 生成 O-(2,6-diphenyl)phenyl N,N-dimethylthiocarbamate
  参考文献：
  名称：

  2,6-二芳基硫酚中的全空间极性π相互作用。

  摘要：

  极性基团与芳香族分子之间的分子识别对于合理的药物设计至关重要。尽管已经公认许多极性官能团通过能量上有利的极性π相互作用与富电子芳族残基相互作用，但对硫醇与芳族体系之间的联系了解甚少。在这里，我们报告了对具有中心硫酚环和两个侧链芳环的2,6-二芳基硫酚进行的物理有机化学研究，这些芳环的电子性质可调节，是由远处对位取代基引起的。哈米特分析显示p K a值和质子亲和力与取代基的哈米特西格玛（Hammett sigma）值密切相关。附加的能量分解分析支持以下结论：贯穿空间的SH-π相互作用和S -- π相互作用均有助于2,6-二芳基硫酚的分子内稳定。

  DOI：

  10.1002/cphc.202000132

文献信息

• A high temperature investigation using microwave synthesis for electronically and sterically disfavoured substrates of the Newman–Kwart rearrangement
  作者：Jonathan D. Moseley、Philip Lenden

  DOI：10.1016/j.tet.2007.02.101

  日期：2007.5

  Electronically deactivated and/or sterically hindered substrates undergo the Newman–Kwart rearrangement (NKR) at around 300 °C, beyond the range of most convenient and safe, small-scale laboratory equipment. We report here the convenient conversions of several difficult substrates using modern microwave technology, which has proven ideal for investigating this high temperature reaction in all but the most

  电子灭活和/或空间受阻的底物会在约300°C的温度下经受Newman-Kwart重排（NKR），这超出了最方便，最安全的小型实验室设备的范围。我们在这里报告了使用现代微波技术可以轻松转换几种困难的底物的方法，事实证明，除最难处理的情况之外，该方法对于研究这种高温反应是理想的选择。另外，重新研究了几个先前报道的困难实例，并且由于阐述的各种原因，发现在这些条件下不需要高温。
• Bulky 2,6-diphenylphenylsulfanyl substituents efficiently inhibit aggregation in phthalocyanines and tetrapyrazinoporphyrazines and control their photophysical and electrochemical properties
  作者：Petr Zimcik、Anna Malkova、Lenka Hruba、Miroslav Miletin、Veronika Novakova

  DOI：10.1016/j.dyepig.2016.09.039

  日期：2017.1

  Octasubstituted zinc, metal-free and magnesium complexes of phthalocyanine and tetrapyrazinoporphyrazine bearing very bulky 2,6-diphenylphenylsulfanyl substituents were synthesized. The substituents efficiently inhibited aggregation of the dyes and only monomers were detected even at a concentration of 200 μM solution in toluene. Photophysical data indicated influence of the heavy-atom effect – magnesium

  合成了带有非常大的2，6-二苯基苯基硫烷基取代基的酞菁和四吡嗪并卟啉的八取代锌，无金属和镁配合物。取代基有效地抑制了染料的聚集，即使在浓度为200μM的甲苯溶液中也仅检测到单体。光物理数据所表示的重原子效应的影响-镁复合物多种荧光（Φ ˚F 0.40-0.51）和锌配合物产生更强的单重态氧（Φ Δ0.56-0.72）。与相应的酞菁类​​似物相比，四吡嗪并卟啉核心中存在额外的氮，使其基本上缺乏电子。2,6-二苯基苯基硫烷基取代基也增加了核心的电子不足特性，并影响了光物理性质。
• Asymmetric zinc phthalocyanines with large steric hindrance as efficient red/near-IR responsive sensitizer for dye-sensitized solar cells
  作者：Lijuan Yu、Wenye Shi、Li Lin、Yingying Guo、Renjie Li、Tianyou Peng

  DOI：10.1016/j.dyepig.2014.11.017

  日期：2015.3

  Asymmetric ZnPc derivatives with two carboxyl and six diphenylphenoxy or diphenylthiophenol groups were synthesized as dye of DSSCs. Those ZnPcs exhibit strong red/near-IR light absorption, and Zn-tri-PcNc-5 with six diphenylthiophenol groups shows obvious redshift in the Q-band and enhanced absorbance compared to Zn-tri-PcNc-4 with six diphenylphenoxy groups, while Zn-tri-PcNc-4 yielded a 3.22% efficiency in sensitizing TiO2-based solar cell, much higher than that (1.30%) of the S-substituted analog (Zn-tri-PcNc-5). The decreased efficiency of Zn-tri-PcNc-5 is due to the molecular orbital shift to negative direction, stemmed from S atoms instead of O atoms in the six substituents of Zn-tri-PcNc-4, which leads to insufficient driving force for the electron injection. The present results demonstrate that the optimization of molecular orbital levels of ZnPcs via changing the substituents' "push-pull" effect is an effective approach to improve the ZnPc-sensitized cell performance. (C) 2014 Elsevier Ltd. All rights reserved.
• Co-ordination chemistry of 2,6-diphenylthiophenol. The syntheses and X-ray crystal structures of some molybdenum and rhodium complexes with σ- or η⁶-phenyl–metal interactions
  作者：Peter T. Bishop、Jonathan R. Dilworth、Terrence Nicholson、Jon Zubieta

  DOI：10.1039/dt9910000385

  日期：——

  Reaction of [MoCl2(CO)4] with the 2,6-diphenylthiophenolate anion (dpt) gives the complex [Mo(eta-6-dpt)(dpt)(CO)], with one thiol phenyl substituent eta-6-bonded to the molybdenum. Crystal data: space group P2(1)/c with a = 13.939(3), b = 10.548(3), c = 20.863(5) angstrom, beta = 106.88(1)-degrees and Z = 4. The eta-6-arene ligand is labile and is reversibly replaced by CO. Replacement of this ligand also occurs with 2,2'-bipyridyl(dipy),1,10-phenanthroline (phen), and 1,2-bis(diphenylphosphino)ethane (dppe) to give the dicarbonyl complexes [Mo(dpt)2(CO)2L] (L = bipy or phen) or the monocarbonyl complex [Mo(dpt)2(CO)(dppe)]. The X-ray crystal structure of the bipy derivative and the mechanism of its formation is discussed. Crystal data: space group P2(1)/c with a = 10.567(3), b = 22.843(5), c = 18.341(3) angstrom, beta = 105.2(2)-degrees and Z = 4. Reaction of RhCl3 with dpt gave the dinuclear species [Rh2mu-SC6H3(C6H4)-2-Ph-6}2(dpt)2(NCMe)2]. An X-ray crystal structure reveals that each bridging thiolate ligand is also sigma-bonded to rhodium [Rh-C 2.016(8) angstrom] via one of the phenyl carbons of the thiolate substituents. Crystal data: space group P2(1)/n, a = 11.991(2), b = 20.426(4), c = 15.910(4) angstrom, beta = 90.42(1) and Z = 2.