2,5-bis(1-phenyl-1-hydroxymethyl)thiophenepyrrole | 179811-42-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: 2,5-bis(1-phenyl-1-hydroxymethyl)thiophenepyrrole
• 英文别名: 2,5-bis[hydroxy(phenyl)methyl]-pyrrole；2,5-bis[hydroxy(phenyl)methyl]pyrrole；2,5-bis(hydroxymethylphenyl)pyrrole；[5-[hydroxy(phenyl)methyl]-1H-pyrrol-2-yl]-phenylmethanol
• CAS: 179811-42-8
• 化学式: C₁₈H₁₇NO₂
• 分子量: 279.338
• InChiKey: GNRZTXFCMNZMCP-UHFFFAOYSA-N

物化性质

• 沸点：
  402.3±14.0 °C(Predicted)
• 密度：
  1.252±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  56.2
• 氢给体数：
  3
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,5-bis(1-phenyl-1-hydroxymethyl)thiophenepyrrole 、 2-[4,5-bis(pentylthio)-1,3-dithiole-2-ylidene]-(1,3)-dithiolo[4,5-c]pyrrole 在 三氟化硼乙醚 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以29 mg的产率得到
  参考文献：
  名称：

  四硫富瓦烯卟啉

  摘要：

  四硫富瓦烯（TTF）-annulated卟啉1 - 4被合成和表征。所有这些都包含四苯基卟啉（TPP）核心，在其上环化了四个，两个或一个TTF亚基。吸收光谱和荧光光谱研究以及电化学研究表明，卟啉系统与环状TTF单元之间的相互作用在溶液中发生。一个或多个TTF单元与卟啉核的环化对与此后一构架相关的还原电势产生深远影响，第一和第二还原电势的正位移分别在0.105至0.355 V和0.200至0.370 V的范围内，分别与模型化合物TPP中的相应过程进行比较18。TTF单元第一次氧化的氧化还原电势在4（ΔE ox 1 = + 0.285 V）和2（ΔE ox 1 = -0.140 V）中有相当大的偏移，而对于1和3，这些电势仍保留在区域内对于正常的TTF单元来说是预期的 与TTF亚基相关联的第二氧化电位相当大的变化被视为对2（Δ ë牛1 = -0.085）和3（Δ ë牛1 = -0.175）。的发射光谱1

  DOI：

  10.1002/chem.200801636
• 作为产物：
  描述：

  甲酮,1H-吡咯-2,5-二基二[苯基- 在 sodium tetrahydroborate 、 lithium bromide 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 1.0h， 生成 2,5-bis(1-phenyl-1-hydroxymethyl)thiophenepyrrole
  参考文献：
  名称：

  四硫富瓦烯卟啉

  摘要：

  四硫富瓦烯（TTF）-annulated卟啉1 - 4被合成和表征。所有这些都包含四苯基卟啉（TPP）核心，在其上环化了四个，两个或一个TTF亚基。吸收光谱和荧光光谱研究以及电化学研究表明，卟啉系统与环状TTF单元之间的相互作用在溶液中发生。一个或多个TTF单元与卟啉核的环化对与此后一构架相关的还原电势产生深远影响，第一和第二还原电势的正位移分别在0.105至0.355 V和0.200至0.370 V的范围内，分别与模型化合物TPP中的相应过程进行比较18。TTF单元第一次氧化的氧化还原电势在4（ΔE ox 1 = + 0.285 V）和2（ΔE ox 1 = -0.140 V）中有相当大的偏移，而对于1和3，这些电势仍保留在区域内对于正常的TTF单元来说是预期的 与TTF亚基相关联的第二氧化电位相当大的变化被视为对2（Δ ë牛1 = -0.085）和3（Δ ë牛1 = -0.175）。的发射光谱1

  DOI：

  10.1002/chem.200801636

文献信息

• Syntheses, Structures, and Coordination Chemistry of Phosphole-Containing Hybrid Calixphyrins:  Promising Macrocyclic P,N₂,X-Mixed Donor Ligands for Designing Reactive Transition-Metal Complexes
  作者：Yoshihiro Matano、Tooru Miyajima、Noriaki Ochi、Takashi Nakabuchi、Motoo Shiro、Yoshihide Nakao、Shigeyoshi Sakaki、Hiroshi Imahori

  DOI：10.1021/ja076709o

  日期：2008.1.1

  Pd(II)-P,N2,S-hybrid complex, in which the calixphyrin platform is regarded as a dianionic ligand. In the complexation with [RhCl(CO)2]2 in dichloromethane, the sigma3-P,N2,S-hybrid behaves as a neutral ligand to afford an ionic Rh(I)-P,N2,S-hybrid complex, whereas the sigma3-P,N2,NH-hybrid behaves as an anionic ligand to produce Rh(III)-P,N3-hybrid complexes. In the latter reaction, it is likely that a

  报道了含磷杂化杯状卟啉（P、N2、X-杂化杯状卟啉）的合成、结构和配位化学及其过渡金属配合物的催化活性。5,10-卟啉二亚甲基 14pi-P,(NH)2,X- 和 16pi-P,N2,X-杂化杯状卟啉（X = O, S, NH）是通过 sigma4-磷酸三吡喃和相应的 2,5-双[羟基（苯基）甲基]杂环，然后进行 DDQ 氧化。杂化杯状卟啉的光谱和晶体学数据都表明，大环平台的构象和大小以及-共轭吡咯-杂-吡咯 (NXN) 单元的氧化态因杂杂的组合而异。sigma3-P,(NH)2,S-和 sigma3-P,N2,S-杂化物与 Pd(OAc)2 和 Pd(dba)2 反应，分别提供相同的 Pd(II)-P,N2,S-杂化复合物，其中将杯状卟啉平台视为双阴离子配体。在二氯甲烷中与 [RhCl(CO)2]2 络合时，sigma3-P,N2,S-杂化物表现为中性配体以提供离子 Rh(I)-P,N2
• Synthesis of meso-tetraphenylthiaporphyrins bearing one inverted pyrrole
  作者：Chang-Hee Lee、Han-Je Kim

  DOI：10.1016/s0040-4039(97)00783-1

  日期：1997.6

  2-Aza-21-thia-23-carba-5,10,15,20-tetraphenylporphyrin and its N-methylated analogue were synthesized and characterized. The synthesis utilizes [3+1] condensation of thiatripyrrin with 2,4-bis(α-hydroxy-α-phenylmethyl)pyrrole or 2,4-bis(α-hydroxy-α-phenylmethyl)-N-methylpyrrole in the presence of acid catalyst. This convenient process gives predominently the titled porphyrin. Reinversion of the pyrrole

  合成并表征了2-Aza-21-thia-23-carba-5,10,15,20-四苯基卟啉及其N-甲基化类似物。该合成利用硫代曲普林与2,4-双（α-羟基-α-苯基甲基）吡咯或2,4-双（α-羟基-α-苯基甲基）-N-甲基吡咯的[3 + 1]缩合。酸催化剂。这种方便的方法主要产生标题为卟啉。通过延长反应时间观察到吡咯单元的反转。
• Synthesis of Thiophene-Containing Hybrid Calixphyrins of the 5,10-Porphodimethene Type
  作者：Yoshihiro Matano、Tooru Miyajima、Noriaki Ochi、Yoshihide Nakao、Shigeyoshi Sakaki、Hiroshi Imahori

  DOI：10.1021/jo800532n

  日期：2008.7.1

  The synthesis, structure, and optical and electrochemical properties of thiophene-containing hybrid calixphyrins are reported. The 5,10-porphodimethene type 14 pi- and 16 pi-S,N(2),X-hybrid calixphyrins (X = NH, O, S) were prepared by acid-promoted dehydrative condensation between a thiatripyrrane and the corresponding 2,5-bis[hydroxy(phenyl)methyl]heteroles followed by DDQ oxidation. Both crystallographic and spectroscopic analyses of the newly prepared hybrid calixphyrins have revealed that the combination of heteroles explicitly influences the electronic structures of the pi-conjugated framework. The 14 pi-S,N(2),X-hybrid calixphyrins have proven to be fluorescent in solution.
• Core-modified porphyrins. Part 6: Effects of lipophilicity and core structures on physicochemical and biological properties in vitro
  作者：Ethel J. Ngen、Thalia S. Daniels、Rajesh S. Murthy、Michael R. Detty、Youngjae You

  DOI：10.1016/j.bmc.2007.12.023

  日期：2008.3.15

  Thiaporphyrins 2-8 were prepared as analogues of 5,20-diphenyl-10,15-bis[4-(carboxymethyleneoxy)-phenyl]-21,23-dithiaporphyrin (1) to examine the effect of structural modifications: substituent changes in meso aryl groups of dithiaporphyrins with one water-solubilizing group (2-5), dihydroxylation of a pyrrole double bond and reduction to dihydroxychlorins (6 and 7), and the removal of two meso aryl groups to give unsubstituted meso positions (8). The impact of these structural modifications was measured in both physicochemical (UV spectra, generation of singlet oxygen, lipophilicity, and aggregate formation) and biological properties (dark toxicity and phototoxicity, cellular uptake, and subeellular localization). Mono-functionalized porphyrins had much higher lipophilicity than di-functionalized porphyrin 1 and, consequently, formed more aggregates in aqueous media. The formation of aggregates might lower the efficiency of lipophilic porphyrins as photosensitizers. Interestingly, dihydroxylation of a core pyrrole group in the dithiaporphyrin core did not affect either the absorption spectrum or the efficiency for generating singlet oxygen. The phototoxicity of dihydroxydithiachlorins mainly depended on their intracellular uptake. The potent phototoxicity of 6, IC50 = 0.18 mu M, was attributed to the extraordinarily high uptake. The intracellular uptake of 6 was about 7.6 times higher than 1. In contrast, thiaporphyrin 8 with only two meso aryl groups was less effective as a photosensitizer, perhaps due to poorer uptake and a lower quantum yield for the generation of singlet oxygen. (C) 2007 Elsevier Ltd. All rights reserved.
• Remarkable Effects of P-Perfluorophenyl Group on the Synthesis of Core-Modified Phosphaporphyrinoids and Phosphadithiasapphyrin
  作者：Takashi Nakabuchi、Yoshihiro Matano、Hiroshi Imahori

  DOI：10.1021/ol100114j

  日期：2010.3.5

  P,X,N-2-type phosphaporphyrins and phosphacalixphyrins (X = N, S) bearing a perfluorophenyl (C6F5) group at the core phosphorus atom were prepared in high overall yield from 1-perfluorophenyl-2,5-di(ethoxycarbonyl)phosphole as a common starting material. In addition, P-C6F5 P,S-2,N-2-type sapphyrin was successfully prepared as the first example of ring-expanded phosphorus-containing porphyrin.