4,4'-di-tert-butyl-1H,1'H-2,2'-bipyrrole | 155858-02-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: 4,4'-di-tert-butyl-1H,1'H-2,2'-bipyrrole
• 英文别名: 4,4'-bis(1,1-dimethylethyl)-2,2'-bi-1H-pyrrole；4,4'-di-t-butyl-2,2'-bipyrrole；4-tert-butyl-2-(4-tert-butyl-1H-pyrrol-2-yl)-1H-pyrrole
• CAS: 155858-02-9
• 化学式: C₁₆H₂₄N₂
• 分子量: 244.38
• InChiKey: XKIVOPMCQDVVTB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  31.6
• 氢给体数：
  2
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  4,4'-di-tert-butyl-1H,1'H-2,2'-bipyrrole 在 copper(I) chloride 、 氯磺酸 、 四氯化钛 、 锌 、 三氯氧磷 作用下， 以 四氢呋喃 为溶剂， 反应 75.0h， 生成 7,17-di-tert-butylporphycene-3,13-disulfonyl chloride
  参考文献：
  名称：

  A red-light-activated sulfonamide porphycene for highly efficient photodynamic therapy against hypoxic tumor

  摘要：

  Photodynamic therapy (PDT) is an emerging alternative cancer treatment modality that utilizes photo-sensitivity to cause cell death upon photo-irradiation. However, PDT efficiency has been hampered by tumor hypoxia, blue-shifted excitation wavelengths, and the high dark toxicity of photo-sensitizers. We designed and synthesized two novel porphycene-based photosensitizers (TBPoS-OH and TBPoS-2OH) with potent photo-cytotoxicity and a LD₅₀ in the nM range under both normoxic and hypoxic conditions in a variety of cell types after photo-irradiation (λ = 640 ± 15 nm). Further studies showed fast-cellular uptake for TBPoS-OH that localized lysosomes and subsequently induced cell apoptosis via the lysosomal-mitochondrial pathway. Moreover, TBPoS-OH significantly reduced tumor growth in two xenografted mouse models bearing melanoma A375 and B16 cells. Finally, TBPoS-OH exhibited no obvious immunogenicity and toxicity to blood cells and major organs in mice. These data demonstrated that these two porphycene-based photosensitizers, especially TBPoS-OH, could be developed as a potential PDT modality.

  DOI：

  10.1016/j.ejmech.2020.112867
• 作为产物：
  描述：

  3-(tert-butyl)-1-(phenylsulfonyl)-1H-pyrrole 在 2,2,6,6-四甲基哌啶 、 氢氧化钾 、 正丁基锂 、 copper dichloride 作用下， 以 甲醇 为溶剂， 反应 11.0h， 生成 4,4'-di-tert-butyl-1H,1'H-2,2'-bipyrrole
  参考文献：
  名称：

  Lausmann, Michael; Zimmer, Ingeborg; Lex, Johann, Angewandte Chemie, 1994, vol. 106, # 7, p. 776 - 779

  摘要：

  DOI：

文献信息

• Hypervalent iodine(III): selective and efficient single-electron-transfer (SET) oxidizing agent
  作者：Toshifumi Dohi、Motoki Ito、Nobutaka Yamaoka、Koji Morimoto、Hiromichi Fujioka、Yasuyuki Kita

  DOI：10.1016/j.tet.2009.10.040

  日期：2009.12

  ethers, affording the corresponding aromatic cation radicals. Since then, hypervalent iodine(III) has been utilized as a selective and efficient SET oxidizing agent that enables a variety of direct C–H functionalizations of aromatic rings in electron-rich arenes under mild conditions. We have now extended the original method to work in a series of heteroaromatic compounds such as thiophenes, pyrroles,

  1994年，我们首先确定了苯基碘（III）双（三氟乙酸盐）（PIFA）对苯基醚的单电子转移（SET）氧化能力，提供了相应的芳族阳离子自由基。从那时起，高价碘（III）已被用作一种选择性和高效的SET氧化剂，可在温和条件下在富电子芳烃中实现芳环的各种直接C–H官能化。现在，我们已经将原始方法扩展为可用于一系列杂芳族化合物，例如噻吩，吡咯和吲哚。本文总结了自本世纪初以来的调查和结果。
• Regioselective Bipyrrole Coupling of Pyrroles and 3-Substituted Pyrroles Using Phenyliodine(III) Bis(trifluoroacetate)
  作者：Yasuyuki Kita、Toshifumi Dohi、Koji Morimoto、Motoki Ito

  DOI：10.1055/s-2007-983798

  日期：2007.9

  A series of electron-rich bipyrroles were prepared by the regioselective, phenyliodine(III) bis(trifluoroacetate) (PIFA) induced oxidative coupling of pyrroles in the presence of bromotrimethylsilane. Using pyrrole and 3,4-disubstituted pyrroles gave exclusively 2,2′-linked bipyrroles without the formation of other bipyrrole regioisomers. The 3-alkyl- or 3-aryl-substituted pyrroles gave unsymmetrical

  在溴代三甲基硅烷存在下，通过区域选择性的苯碘（III）双（三氟乙酸）（PIFA）诱导吡咯的氧化偶联制备了一系列富电子联吡咯。使用吡咯和 3,4-二取代吡咯仅得到 2,2'-连接的联吡咯，而不会形成其他联吡咯区域异构体。3-烷基或3-芳基取代的吡咯以高产率产生不对称的HT二聚体，作为对称HH二聚体上主要的可分离α-连接的联吡咯产物。N-取代基的性质显着影响反应的区域选择性，因此N-苯基-和N-苄基-取代的吡咯的区域控制联吡咯偶联得到2,3'-联吡咯。
• Photophysics of novel 22π porphyrinoids
  作者：Daniel O. Mártire、Sigrid Russell、Hans-Jürgen Dietrich、Carlos J. Cobos、Silvia E. Braslavsky

  DOI：10.1142/s1088424612500496

  日期：2012.5

  The photophysical properties of toluene solutions of two new 22π expanded porphycene compounds were measured using a combination of various steady-state and time-resolved techniques. The determined triplet energy (E T = 109 ± 3) kJ.mol-1, coincident with the calculated E T = (96.0 ± 10) kJ.mol-1, of both red absorbing compounds is higher than the energy required to excite ground state molecular oxygen

  使用各种稳态和时间分辨技术的组合测量了两种新的 22π 膨胀卟啉化合物的甲苯溶液的光物理性质。确定的三重态能量（E吨= 109 ± 3) kJ.mol-1，与计算的 E 一致吨= (96.0 ± 10) kJ.mol-1，两种红色吸收化合物的能量都高于将基态分子氧激发为单线态分子氧所需的能量。然而，系统间杂交产量非常低（约 10-2)，这使得这些化合物成为较差的光敏剂。两种扩展的 22π 卟啉化合物的三重态产率远低于母体卟啉的产率，而它们的荧光与卟啉的值一样高（约 30%）。这两种新化合物对卟啉三重态的扩散猝灭速率常数比扩散猝灭速率常数慢，这反映了放热能量转移的空间阻碍因素。