2,5-bis-(4-nitro-phenyl)-[1,4]dithiine | 38172-60-0

• 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: 2,5-bis-(4-nitro-phenyl)-[1,4]dithiine
• 英文别名: 2,5-bis(4-nitrophenyl)-1,4-dithiine
• CAS: 38172-60-0
• 化学式: C₁₆H₁₀N₂O₄S₂
• 分子量: 358.398
• InChiKey: PTCJODTWSGSVEY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  142
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2,5-bis-(4-nitro-phenyl)-[1,4]dithiine 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 反应 6.0h， 以50%的产率得到2,6-bis(p-nitrophenyl)-1,4-dithiafulvene
  参考文献：
  名称：

  关于1，4-二硫辛环缩合成1，3-二硫醇衍生物的研究

  摘要：

  讨论了不同的因素（碱的p K a，抗衡离子的性质和离子对的解离）对碱诱导的1，4-二硫辛素重排成1，3-二硫醇衍生物的过程的影响。从头算起就说明了这些异构化的驱动力。

  DOI：

  10.1016/s0040-4039(00)02147-x

文献信息

• The Dimerization of 2,5-Diaryl-1,4-dithiin Radical Cations.
  作者：Mogens Larsen Andersen、Merete Folmer Nielsen、Ole Hammerich、Anne Kjersti Bakken、S. U. Pedersen、Lauri Niinistö、Stenbjörn Styring、Cecilia Tommos、Kurt Warncke、Bryan R. Wood

  DOI：10.3891/acta.chem.scand.51-0094

  日期：——

  The electrochemical oxidation of five 2,5-diaryl-1,4-dithiins with aryl=p-anisyl (BAD), p-tolyl (BTD), phenyl (DPD), p-chlorophenyl (BCD) and p-nitrophenyl (END) has been studied in MeCN-CH2Cl2 (1:1) by cyclic voltammetry (CV), derivative cyclic voltammetry (DCV) and linear sweep voltammetry (LSV) as well as constant current coulometry and product analyses. All compounds were found to undergo two quasi-reversible one-electron transfers to the radical cations and the dications. The formal potential of the first redox couple and the life-time of the radical cation were found to decrease when the aryl group became more electron donating. The radical cation of END was non-reactive on the timescale of slow-scan CV, whereas the radical cation of BAD was so reactive that it was impossible to outrun the follow-up reaction even at a scan rate of 1000 V s(-1). The number of electrons determined in the presence of 2,6-lutidine, added to prevent acid-catalyzed conversion of substrate, was between 1.1 and 1.5 except for END, the radical cation of which catalyzed the oxidation of some unknown species in the solution. The major products from preparative electrolysis were the corresponding 2,2'-dimers, which were isolated in yields up to 20%. A detailed mechanistic and kinetic analysis of the dimerization, in the presence of 2,6-lutidine, involving the simultaneous fitting of theoretical data and experimental data obtained by LSV and DCV on a timescale covering several orders of magnitude, demonstrated that the process was of the radical cation-radical cation type and allowed for the determination of rate and equilibrium constants, k(1) and K-1. In addition, the values of the heterogeneous electron transfer rate constant, k(8), and the transfer coefficient, alpha, could be determined this way. The values of k(1) were found to vary between 2.2x10(6) M(-1) s(-1) (BAD) and 8.7 x 10(2) M(-1) s(-1) (BCD). The Hammett-plot, log k(1) vs. sigma(+), was linear indicating the importance of resonance stabilization for the dicationic transition state. The formal potentials for the reversible oxidation of the 2,2'-dimers to the radical cations were 70-120 mV higher than those for the monomers although AMI calculations predicted the ionization potentials of the dimers to be slightly lower than those for monomers. It is suggested that differences in solvation more than counterbalance the purely electronic effects.
• Andersen, Morgens Larsen; Nielsen, Merete Folmer; Hammerich, Ole, Acta Chemica Scandinavica, 1995, vol. 49, # 7, p. 503 - 514
  作者：Andersen, Morgens Larsen、Nielsen, Merete Folmer、Hammerich, Ole

  DOI：——

  日期：——
• US4265807A
  申请人：——

  公开号：US4265807A

  公开（公告）日：1981-05-05
• On the ring-contraction of 1,4-dithiins to 1,3-dithiole derivatives
  作者：Raquel Andreu、Javier Garı́n、Jesús Orduna、José M Royo

  DOI：10.1016/s0040-4039(00)02147-x

  日期：2001.1

  The effect of different factors (pKa of the base, nature of the counterion and dissociation of the ion pairs) on the course of the base-induced rearrangement of 1,4-dithiins to 1,3-dithiole derivatives is discussed. Ab initio calculations account for the driving force of these isomerisations.

  讨论了不同的因素（碱的p K a，抗衡离子的性质和离子对的解离）对碱诱导的1，4-二硫辛素重排成1，3-二硫醇衍生物的过程的影响。从头算起就说明了这些异构化的驱动力。