N⁴,N⁵,N^4',N^5'-Tetrakis-(3-trifluoromethyl-phenyl)-[2,2']biimidazolylidene-4,5,4',5'-tetraamine | 189115-08-0

• 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: N⁴,N⁵,N^4',N^5'-Tetrakis-(3-trifluoromethyl-phenyl)-[2,2']biimidazolylidene-4,5,4',5'-tetraamine
• 英文别名: 2-[4,5-bis[3-(trifluoromethyl)anilino]imidazol-2-ylidene]-4-N,5-N-bis[3-(trifluoromethyl)phenyl]imidazole-4,5-diamine
• CAS: 189115-08-0
• 化学式: C₃₄H₂₀F₁₂N₈
• 分子量: 768.567
• InChiKey: OFBRDCQCZZQTIT-UHFFFAOYSA-N

物化性质

• 沸点：
  606.5±65.0 °C(Predicted)
• 密度：
  1.53±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8
• 重原子数：
  54
• 可旋转键数：
  8
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  97.6
• 氢给体数：
  4
• 氢受体数：
  16

反应信息

• 作为反应物：
  描述：

  N⁴,N⁵,N^4',N^5'-Tetrakis-(3-trifluoromethyl-phenyl)-[2,2']biimidazolylidene-4,5,4',5'-tetraamine 在 三氟化硼乙醚 、 三乙胺 作用下， 以 甲苯 为溶剂， 反应 0.5h， 以81%的产率得到1,1',3,3'-tetrakis[3-(trifluoromethyl)phenyl]-2,2,2',2'-tetrafluoro-2,2',4,4'-tetrahydro-1H,1'H-2λ⁴,2'λ⁴-[5,5']bi[2-bora-1,3,4,6-tetraaza-pentalenylidene]
  参考文献：
  名称：

  New tetraazafulvadienes via cascade reactions and their cyclizations to diazaborolidines

  摘要：

  3,4,5,6-Tetrahydro-2-aminopyridine reacts with bis-imidoylchlorides derived from oxalic acid to yield new dimeric tetraazafulvadienes. Ketene aminals could be isolated and characterized as key intermediates in a cascade reaction (cyclization-prototropism-oxidation-dimerization-deprotonation). The stable tetraazafulvadienes have been transformed with boron compounds into highly fluorescent tricyclic diazaborolidines. (C) 2004 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tet.2004.03.012

文献信息

• Highly Fluorescent Heterocycles Based on Pyrazino Fused 1,4,5,8-Tetra-azafulvalenes
  作者：Rainer Beckert、Christian Käpplinger、Jan Koci、Gabriela Braunerova、Karel Waisser、Helmar Görls

  DOI：10.3987/com-03-9842

  日期：——

  Some new pyrazino-fused 1,4,5,8-tetraazafulvalenes of type (3-5) were synthesized and their structures were confirmed by IR, UV-VIS, 1 H NMR spectra and elemental analysis. The X-Ray crystal structure analysis of a singlecrystal of derivative (3c) revealed a nearly ideal planarized heterofulvalene subunit. The new prepared tricyclic tetraazafulvalenes of type (3) show strong red fluorescence at 605

  合成了一些新型吡嗪稠合1,4,5,8-四氮杂富瓦烯(3-5)，并通过IR、UV-VIS、1 H NMR光谱和元素分析证实了它们的结构。衍生物 (3c) 的单晶的 X 射线晶体结构分析揭示了一个近乎理想的平面化异富瓦烯亚基。新制备的 (3) 型三环四氮杂富瓦烯在 605 nm 处显示出强烈的红色荧光。
• Polyazaacenes – On the Way to Stable, Fluorescent and Redox-Active Derivatives
  作者：Frances Stöckner、Rainer Beckert、Dieter Gleich、Eckhard Birckner、Wolfgang Günther、Helmar Görls、Gavin Vaughan

  DOI：10.1002/ejoc.200600803

  日期：2007.3

  polyazaacenes is described starting from two different nucleophilic building blocks. Disubstituted oxalic amidines 1 can be cyclized under mild conditions with 2,3-dichloro-5,6-dicyanopyrazine (3) to yield 5,6-dihydropyrazino[2,3-b]pyrazines 4a–c. By employing higher temperatures and 2 equiv. of 3, octaazanaphthacene 6 can be isolated. Similarly, pyrazino[2,3-b]pyrazines 2 and bielectrophile 3 yielded novel

  描述了一种从两种不同的亲核结构单元开始制备聚氮杂并苯的新合成方法。双取代的草酸脒 1 可以在温和条件下与 2,3-二氯-5,6-二氰基吡嗪 (3) 环化，得到 5,6-二氢吡嗪并 [2,3-b] 吡嗪 4a-c。通过采用更高的温度和 2 当量。3、八氮杂萘6可以被分离出来。类似地，除了半环化衍生物 9 之外，吡嗪并 [2,3-b] 吡嗪 2 和双亲电子试剂 3 还产生了新的十二氮杂六苯 8。当四氮杂富瓦烯 10d 在二甲苯中在氧气存在的情况下加热时，八氮杂六苯 13 分离为主要产品。代替吡嗪并[2,3-b]吡嗪2，这种高度荧光的聚氮杂并苯是通过级联反应形成的，该反应涉及一个dytropic重排，分子内 Diels-Alder 反应和多步氧化还原反应。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
• Dyotropic Rearrangements of Tetraazafulvalenes - A New Approach to ­Aminosubstituted 1,4,5,8-Tetraazanaphthalenes
  作者：Rainer Beckert、Frances Stöckner、Christian Käpplinger、Helmar Görls

  DOI：10.1055/s-2005-863708

  日期：——

  Tetraazafulvalenes 1 rearrange in the presence of Montmorillonite-clay to give strongly fluorescent 1,4,5,8-tetraazanaphthalenes of type 2. This observation agrees with that reported for the cross-conjugated systeme of indigo, thus indicating a dyotropic rearrangement has taken place. Inclusion of the extended π-electron-systeme of 1 should facilitate this symmetry forbidden [σ2+σ2]-process. Based on these results, some reactions of heterofulvalenes and -fulvenes reported in the literature can now be explained by dyotropic rearrangements. The easy rearrangement of 1 in the presence of K10 and DMF opens the way for the synthesis of hard to obtain ring-fused pyrazines of type 2.

  四氮杂萘 1 在蒙脱石-粘土的作用下发生重排，生成了具有强烈荧光的 1,4,5,8-四氮杂萘 2。这一观察结果与靛蓝交叉共轭体系的观察结果一致，从而表明发生了向色性重排。1 的扩展Ï-电子体系的加入应该会促进这种对称禁止的 [Ï2+Ï2]-过程。基于这些结果，文献中报道的一些杂富勒烯和富勒烯的反应现在可以用向性重排来解释。1 在 K10 和 DMF 存在下的简易重排为合成难以获得的 2 型环融吡嗪开辟了道路。
• Stabile Tetraazafulvalene - Synthesen und Folgechemie
  作者：Christian K�pplinger、Rainer Beckert、Wolfgang Imhof

  DOI：10.1002/prac.19983400406

  日期：——

  The syntheses, properties and reactions are described for 1,3,6,7-tetrakis[arylamino]-1,4,5,8-tetraazafulvalenes and their vinylogous derivatives. First, the acylation of form-as well as acetamidine with bis-imidoylchlorides derived from oxalic acid 6 formed reactive cyclic intermediates which dimerized to tetraazafulvalenes 12 or bisvinylogous tetraazafulvalenes 14. Based on, a further synthesis was found using a cycloacylation reaction of amidines with imidoylchlorides 6 followed by prototropic migration of alpha-hydrogen. Thus, the vinylogous compound 15 and the phenylogous derivatives 16, 17 could be isolated in moderate up to good yields. Besides amidines, other derivatives of carboxylic acids as amides or thioamides could be transformed into corresponding tetraazafulvalenes 18-20. Due to their vicinal amino groups, alkylation and acylation reactions were studied. For example, the reaction with orthoformates yielded the ring fused products 24a,b which may be starting material for carbenes just as the cyclization product with thiophosgene 27. Treatment of tetraazafulvalenes with anhydrous iron-II salts or molybdenum hexacarbonyl yielded the deeply colored metal diazadiene complexes 33 and 34. Finally, reduction using metallic lithium and subsequent alkylation constitutes a convenient synthetic entry to heterocyclic analogues of stilbene 37.
• Kapplinger; Beckert, Synlett, 2000, # 11, p. 1679 - 1681
  作者：Kapplinger、Beckert

  DOI：——

  日期：——