5,5-dimethyl-1,9-bis(pentafluorobenzoyl)dipyrromethane | 942041-83-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5,5-dimethyl-1,9-bis(pentafluorobenzoyl)dipyrromethane
• 英文别名: [5-[2-[5-(2,3,4,5,6-pentafluorobenzoyl)-1H-pyrrol-2-yl]propan-2-yl]-1H-pyrrol-2-yl]-(2,3,4,5,6-pentafluorophenyl)methanone
• CAS: 942041-83-0
• 化学式: C₂₅H₁₂F₁₀N₂O₂
• 分子量: 562.367
• InChiKey: BGOZBLOYWMMGLU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  39
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  65.7
• 氢给体数：
  2
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  5,5-dimethyl-1,9-bis(pentafluorobenzoyl)dipyrromethane 在 sodium tetrahydroborate 、 三氟乙酸 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 2.83h， 生成 5,5-dimethyl-10,20-bis(pentafluorophenyl)-15-(2,6-dimethoxyphenyl)phlorin
  参考文献：
  名称：

  显示协同氟化物结合的 Phlorin 大环化合物家族的合成、电化学和光物理学

  摘要：

  已经制备了一组同源的 5,5-二甲基叶绿素大环，其中一个芳环的身份系统地变化。这些衍生物含有辅助的五氟苯基 (3H(Phl(F)))、均三甲苯 (3H(Phl(Mes)))、2,6-双甲氧基苯基 (3H(Phl(OMe)))、4-硝基苯基 (3H(Phl(NO2)) ))) 或 4-叔丁基羧基苯基 (3H(Phl(CO2tBu))) 基团位于 15-中间位。这些类卟啉以良好的产率 (35-50%) 制备，并显示出不寻常的多电子氧化还原和光化学性质。每种根皮素在适度的电位下最多可被氧化 3 次，并可被还原 2 次。辅助芳基取代基的给电子和放电子特性减弱了这些氧化还原事件的电位；含有供电子芳基的根皮素更容易氧化，更难还原，而含有吸电子功能的根皮素则观察到相反的趋势。Phlorin 取代对观察到的光物理学也有明显的影响，因为在大环的外围引入释放电子的芳基，可以产生更大的发射量子产率和更长的荧光寿

  DOI：

  10.1021/ja401391z
• 作为产物：
  描述：

  2,2'-(2,2-丙烷二基)二(1H-吡咯) 、 五氟苯甲酰氯 在 乙基溴化镁 作用下， 以30%的产率得到5,5-dimethyl-1,9-bis(pentafluorobenzoyl)dipyrromethane
  参考文献：
  名称：

  10,10-二甲基双二烯锌铜配合物的电化学、光谱和 1O2 敏化特性

  摘要：

  介绍了在 5- 和 15-内消旋位置 ( DMBil1 )带有辅助五氟苯基的10,10-二甲基双二烯四吡咯的合成、电化学和光物理表征。这种非大环四吡咯平台非常坚固，可作为 Zn 2+和 Cu 2+中心的出色配体支架。对DMBil1以及相应的Zn[DMBil1]和Cu[DMBil1]进行的 X 射线衍射研究复合物表明该配体支架结合四吡咯核心内的单个金属离子。此外，电化学实验表明，所有上述三种化合物都显示出有趣的氧化还原化学，因为DMBil1框架可以被两个电子氧化和还原。对DMBil1、Zn[DMBil1]和Cu[DMBil1]进行的光谱和光物理实验提供了这些平台的电子特性的基本图片。所有三种双二烯衍生物都强烈吸收可见光区域的光，并且发射微弱。这些化合物敏化1 O 2形成的能力在波长超过 500 nm 的情况下进行了探测。游离碱和 Zn 2+ 10,10-二甲基双二烯结构均显示出适度的1 O

  DOI：

  10.1021/jp506412r

文献信息

• Photochemotherapeutic Properties of a Linear Tetrapyrrole Palladium(II) Complex displaying an Exceptionally High Phototoxicity Index
  作者：Andrea M. Potocny、Rachel S. Riley、Rachel K. O’Sullivan、Emily S. Day、Joel Rosenthal

  DOI：10.1021/acs.inorgchem.8b01225

  日期：2018.9.4

  In PDT, photosensitizers embedded within tumors are activated by light and undergo intersystem crossing, followed by energy transfer to molecular oxygen, resulting in the production of toxic singlet oxygen (1O2). Previously, we reported a robust, linear tetrapyrrole palladium(II) complex, Pd[DMBil1], characterized by its facile and modular synthesis, broad absorption profile, and efficient 1O2 quantum

  光动力疗法（PDT）代表了一种微创且高度局部化的治疗策略，可消融几乎没有副作用的肿瘤。在PDT中，嵌入在肿瘤中的光敏剂会被光激活并进行系统间交换，然后将能量转移到分子氧中，从而产生有毒的单线态氧（1 O 2）。先前，我们报道了一个强大，线性四吡咯钯（II）络合物，PD [DMBil1] ，其特征在于它的轻便和模块化合成，宽的吸收曲线，高效1 Ò 2 Φ的量子产率Δ= 0.8（在有机媒体中）。然而，该卟啉类衍生物在水溶液中的不溶性阻止了其在生物学相关条件下的使用。在这项工作中，我们报告了Pd [DMBil1] -PEG 750的合成，Pd [DMBil1] -PEG 750是一种水溶性的二甲基双二烯衍生物，具有聚乙二醇（PEG）官能团。该复合物的表征表明，在生物学相关条件下，这种聚乙二醇化的二甲苯结构保持了母体复合物的诱人光物理性质。更具体地，该吸收曲线的Pd [DMBil1] -PEG 750紧密匹配的PD
• Synthesis, structure, electronic characterization, and halogenation of gold(III) phlorin complexes
  作者：Allen J. Pistner、Maxwell I. Martin、Glenn P.A. Yap、Joel Rosenthal

  DOI：10.1142/s1088424621500565

  日期：2021.7

  metalloporphyrins, rather than direct metalation of freebase phlorin constructs. In this work, an alternate synthetic approach for preparation of gold(III) phlorin complexes that involves the first direct metalation of two different freebase phlorin derivatives (3H(PhltBu) and 3H(PhlF)) with AuBr3 to produce the stable and fully isolable gold(III) phlorin complexes Au(PhltBu) and Au(PhlF) is reported. The first

  Phlorin 的金属化化学，它是一种非芳族四吡咯大环，含有一个单一的sp与更传统的四吡咯如卟啉、corroles 和酞菁相比，3-杂化中间碳仍然不发达。制备金属卟啉的先前努力很少，并且已报道的那些依赖于母体金属卟啉的还原或亲核攻击，而不是游离碱金属卟啉结构的直接金属化。在这项工作中，一种制备金 (III) 根皮素配合物的替代合成方法涉及两种不同的游离碱根皮素衍生物 (3H(Phl) 的第一次直接金属化。叔丁基醚)和 3H(PhlF))与 AuBr 3产生稳定且完全可分离的金 (III) phlorin 配合物 Au(Phl叔丁基醚)和 Au(PhlF)被报道。具有双二甲基取代基的金属卟啉在sp3-杂化中观-碳通过还报道了 X 射线晶体学。除了制备 Au(Phl叔丁基醚)和 Au(PhlF)，还详细介绍了这两种金 (III) phlorin 与其游离碱同系物相比的紫外可见吸收和氧化还原特性
• Internally 1,4-Phenylene-Bridgedmeso Aryl-Substituted Expanded Porphyrins: The Decaphyrin and Octaphyrin Cases
  作者：Venkataramanarao G. Anand、Shohei Saito、Soji Shimizu、Atsuhiro Osuka

  DOI：10.1002/anie.200502769

  日期：2005.11.11
• Phlorins Bearing Different Substituents at the sp³-Hybridized Meso-Position
  作者：Alexandra M. Bruce、Emily S. Weyburne、James T. Engle、Christopher J. Ziegler、G. Richard Geier

  DOI：10.1021/jo5008256

  日期：2014.6.20

  Phlorins bearing different substituents at the sp(3)-hybridized meso-position were investigated. The extent to which different substituents at this unique position can influence phlorin spectroscopic properties, structure, and stability is of interest given that such substituents are not in direct conjugation with the phlorin macrocycle. While the effect of various substituents at the sp(2)-hybridized positions has been the subject of prior investigations, the impact of different substituents at the saturated carbon atom has not been systematically examined. In this study, phlorins with different combinations of geminal methyl and phenyl substituents were prepared in yields of 24-49% via dipyrromethane + dipyrromethanedicarbinol routes, and their NMR spectra, UV vis spectra, X-ray crystal structures, and stability toward light and air were compared. The nature of the substituents at the sp(3)-hybridized position was found to impact spectroscopic properties, structure, and stability to varying degrees. Thus, the choice of substituents at the sp(3)-hybridized meso-position provides a further option for altering phlorin properties.
• Dipyrromethane + Dipyrromethanedicarbinol Routes to an Electron Deficient meso-Substituted Phlorin with Enhanced Stability
  作者：Anna Y. O'Brien、John P. McGann、G. Richard Geier

  DOI：10.1021/jo070216k

  日期：2007.5.1

  Two dipyrromethane + dipyrromethanedicarbinol routes to a meso-substituted phlorin bearing electron-withdrawing pentafluorophenyl substituents (TpFPPhl) were investigated in an attempt to obtain a phlorin with enhanced stability toward light and air and to explore the application of dipyrromethanecarbinol chemistry to the preparation of phlorins. For each route, a systematic survey of reaction parameters for the two-step, one-flask reaction leading to TpFPPhl was performed. The analytical-scale reactions were monitored for yield of TpFPPhl by HPLC. Sharp differences were observed in the yield of TpFPPhl afforded by the two synthetic routes. The most promising reaction condition (TFA catalysis, 100 mM) was performed on a preparative scale providing TpFPPhl in a yield of 45% (189 mg). The stability of the electron-deficient phlorin in dilute solution upon exposure to light and air was probed in a number of solvents, and decomposition was monitored by UV-vis spectroscopy and HPLC. Many of the solutions of TpFPPhl were found to be quite stable for periods of similar to 8 h, with decomposition requiring exposure periods of several days. Taken together, this work contributes an efficient synthesis of a meso-substituted phlorin of practical stability and provides further insights toward the adaptation of dipyrromethanecarbinol chemistry to the preparation of diverse porphyrinoids.