(5-{1-[5-(Hydroxy-pentafluorophenyl-methyl)-1H-pyrrol-2-yl]-1-methyl-ethyl}-1H-pyrrol-2-yl)-pentafluorophenyl-methanol | 873840-21-2

• 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: (5-{1-[5-(Hydroxy-pentafluorophenyl-methyl)-1H-pyrrol-2-yl]-1-methyl-ethyl}-1H-pyrrol-2-yl)-pentafluorophenyl-methanol
• 英文别名: [5-[2-[5-[hydroxy-(2,3,4,5,6-pentafluorophenyl)methyl]-1H-pyrrol-2-yl]propan-2-yl]-1H-pyrrol-2-yl]-(2,3,4,5,6-pentafluorophenyl)methanol
• CAS: 873840-21-2
• 化学式: C₂₅H₁₆F₁₀N₂O₂
• 分子量: 566.398
• InChiKey: TXEHEPKHQRQMOG-UHFFFAOYSA-N

物化性质

• 沸点：
  566.9±45.0 °C(Predicted)
• 密度：
  1.587±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  39
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  72
• 氢给体数：
  4
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  (5-{1-[5-(Hydroxy-pentafluorophenyl-methyl)-1H-pyrrol-2-yl]-1-methyl-ethyl}-1H-pyrrol-2-yl)-pentafluorophenyl-methanol 、 5-苯基联吡咯甲烷 在 三氟乙酸 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 二氯甲烷 为溶剂， 以49%的产率得到5,5-dimethyl-10,15,20-tris(pentafluorophenyl)phlorin
  参考文献：
  名称：

  Phlorins Bearing Different Substituents at the sp³-Hybridized Meso-Position

  摘要：

  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.

  DOI：

  10.1021/jo5008256
• 作为产物：
  描述：

  5,5-dimethyl-1,9-bis(pentafluorobenzoyl)dipyrromethane 在 sodium tetrahydroborate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 2.0h， 生成 (5-{1-[5-(Hydroxy-pentafluorophenyl-methyl)-1H-pyrrol-2-yl]-1-methyl-ethyl}-1H-pyrrol-2-yl)-pentafluorophenyl-methanol
  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

文献信息

• Electrochemical, Spectroscopic, and ¹O₂ Sensitization Characteristics of 10,10-Dimethylbiladiene Complexes of Zinc and Copper
  作者：Allen J. Pistner、Rachel C. Pupillo、Glenn P. A. Yap、Daniel A. Lutterman、Ying-Zhong Ma、Joel Rosenthal

  DOI：10.1021/jp506412r

  日期：2014.11.13

  The synthesis, electrochemistry, and photophysical characterization of a 10,10-dimethylbiladiene tetrapyrrole bearing ancillary pentafluorophenyl groups at the 5- and 15-meso positions (DMBil1) is presented. This nonmacrocyclic tetrapyrrole platform is robust and can serve as an excellent ligand scaffold for Zn2+ and Cu2+ centers. X-ray diffraction studies conducted for DMBil1 along with the corresponding

  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
• 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
• 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.