9,11,20,22-四氢四苯并[d,f,k,m][1,3,8,10]四氮杂十四环-10,21-二硫酮 | 221011-41-2

• 物质功能分类: 分析化学 - 分析试剂 - 常用分析试剂
• 分子结构分类: 有机化合物 - 苯类化合物
• 中文名称: 9,11,20,22-四氢四苯并[d,f,k,m][1,3,8,10]四氮杂十四环-10,21-二硫酮
• 中文别名: 9,11,20,22-四氢四苯并[d,f,k,m][1,3,8,10]四氮杂十四环-10,21-二硫酮
• 英文名称: Nitrate Ionophore V
• 英文别名: 8,10,23,25-tetrazapentacyclo[24.4.0.02,7.011,16.017,22]triaconta-1(30),2,4,6,11,13,15,17,19,21,26,28-dodecaene-9,24-dithione
• CAS: 221011-41-2
• 化学式: C₂₆H₂₀N₄S₂
• 分子量: 452.604
• InChiKey: GVMHPPQEENVYSW-UHFFFAOYSA-N

物化性质

• 沸点：
  652.1±61.0 °C(Predicted)
• 密度：
  1.40±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  32
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  112
• 氢给体数：
  4
• 氢受体数：
  2

安全信息

• 危险品标志：
  Xi
• 安全说明：
  S26
• 危险类别码：
  R36/37/38

反应信息

• 作为反应物：
  描述：

  9,11,20,22-四氢四苯并[d,f,k,m][1,3,8,10]四氮杂十四环-10,21-二硫酮 在 magnesium sulfate 、 mercury(II) oxide 作用下， 以 苯 为溶剂， 反应 84.0h， 以7%的产率得到bis<1,3>diazepino>-1,3-diazetidine
  参考文献：
  名称：

  Preparation and Intramolecular Cyclization of Bis(carbodiimides). Synthesis and X-ray Structure of 1,3-Diazetidine-2,4-diimine Derivatives

  摘要：

  Aza-Wittig reactions of bis(iminophosphorane) 1 derived from 2,2'-diazidobiphenyl with aromatic isocyanates provided dibenzo[d,f]-1,3-diazetidino[1,2-a]diazepine derivatives 2 in moderate yields. Similar results can be achieved from the reaction of 2,2'-bis(isothiocyanato)biphenyl 4 with aryliminophosphoranes. Treatment of bis(isothiocyanate) 4 with arylamines and further dehydrosulfurization of the resulting bis(thioureas) leads to the seven-membered ring guanidines 8. N-2-(2'-Azido)biphenyI-N'-arylcarbodiimides 13 react with 1 equiv of triphenylphosphane to give zwitterionic compounds 15, which undergo either hydrolytic cleavage to afford the guanidines 8 or react with 1 equiv of aromatic isocyanates to provide 2. Cross-experiments suggest that the: conversion 15 --> 2 takes place through a nonisolable bis(carbodiimide) that undergoes an intramolecular [2 + 2] cycloaddition at the final step. The reaction of bis(iminophosphorane) 1 with an excess of carbon dioxide leads to a mixture of the tricyclic 1,3-diazetidine derivative 6 and the 14-membered cyclic bis(carbodiimide) 23, which decomposes by thermal treatment. Compound 6 can also be obtained along with the seven-membered cyclic urea derivatives 24 from the reaction of bis(iminophosphorane) 1 with the carbon dioxide source Boc(2)O/DMAP system. A comprehensive mechanistic scheme for the aza-Wittig reactions studied is conveniently presented. The molecular and crystal structures of 1-(4-methoxyphenyl)-2-(4-methoxyphenyl)iminodibenzo[d,f]-1,3-diazetidino-[1,2-a]diazepine (2c) and [a,c]bis[dibenzo[d,f][1,3]diazepino]-1,3]diazepino]-1,3-diazetidine (6) have been determined by X-ray analysis.

  DOI：

  10.1021/jo981339v
• 作为产物：
  描述：

  2,2-联苯二胺 在 potassium carbonate 作用下， 以 氯仿 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 24.5h， 生成 9,11,20,22-四氢四苯并[d,f,k,m][1,3,8,10]四氮杂十四环-10,21-二硫酮
  参考文献：
  名称：

  Preparation and Intramolecular Cyclization of Bis(carbodiimides). Synthesis and X-ray Structure of 1,3-Diazetidine-2,4-diimine Derivatives

  摘要：

  Aza-Wittig reactions of bis(iminophosphorane) 1 derived from 2,2'-diazidobiphenyl with aromatic isocyanates provided dibenzo[d,f]-1,3-diazetidino[1,2-a]diazepine derivatives 2 in moderate yields. Similar results can be achieved from the reaction of 2,2'-bis(isothiocyanato)biphenyl 4 with aryliminophosphoranes. Treatment of bis(isothiocyanate) 4 with arylamines and further dehydrosulfurization of the resulting bis(thioureas) leads to the seven-membered ring guanidines 8. N-2-(2'-Azido)biphenyI-N'-arylcarbodiimides 13 react with 1 equiv of triphenylphosphane to give zwitterionic compounds 15, which undergo either hydrolytic cleavage to afford the guanidines 8 or react with 1 equiv of aromatic isocyanates to provide 2. Cross-experiments suggest that the: conversion 15 --> 2 takes place through a nonisolable bis(carbodiimide) that undergoes an intramolecular [2 + 2] cycloaddition at the final step. The reaction of bis(iminophosphorane) 1 with an excess of carbon dioxide leads to a mixture of the tricyclic 1,3-diazetidine derivative 6 and the 14-membered cyclic bis(carbodiimide) 23, which decomposes by thermal treatment. Compound 6 can also be obtained along with the seven-membered cyclic urea derivatives 24 from the reaction of bis(iminophosphorane) 1 with the carbon dioxide source Boc(2)O/DMAP system. A comprehensive mechanistic scheme for the aza-Wittig reactions studied is conveniently presented. The molecular and crystal structures of 1-(4-methoxyphenyl)-2-(4-methoxyphenyl)iminodibenzo[d,f]-1,3-diazetidino-[1,2-a]diazepine (2c) and [a,c]bis[dibenzo[d,f][1,3]diazepino]-1,3]diazepino]-1,3-diazetidine (6) have been determined by X-ray analysis.

  DOI：

  10.1021/jo981339v

文献信息

• Exploring the Conversion of Macrocyclic 2,2′-Biaryl Bis(thioureas) into Cyclic Monothioureas: An Experimental and Computational Investigation
  作者：Mateo Alajarin、Carmen Lopez-Leonardo、Raul-Angel Orenes、Aurelia Pastor、Pilar Sanchez-Andrada、Angel Vidal

  DOI：10.1021/acs.joc.8b02496

  日期：2018.11.16

  Macrocyclic bis(thioureas) derived from 2,2′-biphenyl and binaphthyl skeletons have been synthesized by reaction of 2,2′-diaminobiaryl and 2,2′-bis(isothiocyanato)biaryl derivatives. The splitting of these bis(thioureas) into two units of the respective cyclic monothioureas has been monitored by NMR, shedding some light on the factors that control these processes. Additionally, a computational study

  通过2,2'-二氨基联芳基和2,2'-双（异硫氰酸根合）联芳基衍生物的反应合成了衍生自2,2'-联苯和联萘骨架的大环双（硫脲）。已通过NMR监测了这些双（硫脲）分裂成两个环状单硫脲的单元，从而为控制这些过程的因素提供了一些线索。此外，一项计算研究还揭示了将3，2'-联苯衍生的双（硫脲）转化为相应的单硫脲的多达三种机理。所提出的机制将水分子的参与作为一种有效的质子转换以及不同类别的假定中间体。计算研究还支持了硫脲基团参与过多过程（如质子平衡，顺式⇆反式异构化。