meso-ethyl-di(1H-pyrrol-2-yl)methane | 351884-77-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: meso-ethyl-di(1H-pyrrol-2-yl)methane
• 英文别名: 5-ethyldipyrromethane；1,1-Dipyrrolpropane；2-[1-(1H-pyrrol-2-yl)propyl]-1H-pyrrole
• CAS: 351884-77-0
• 化学式: C₁₁H₁₄N₂
• 分子量: 174.246
• InChiKey: PZDLFASMQGKWJO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 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：

  meso-ethyl-di(1H-pyrrol-2-yl)methane 在 potassium carbonate 、 三氟乙酸 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 58.0h， 生成
  参考文献：
  名称：

  卟啉-DNA交联剂杂化物：化学合成和生物学研究。

  摘要：

  已经合成了三种新的卟啉-DNA交联缀合物8、9和10。已经研究了它们的光诱导DNA切割活性。卟啉衍生物8、9和10在光照射下对THP-1细胞的IC（50）值分别为5.6、88.4和61.8 nM。

  DOI：

  10.1016/j.bmcl.2004.04.044
• 作为产物：
  描述：

  2-吡咯甲醛 以 乙醚 为溶剂， 反应 0.16h， 生成 meso-ethyl-di(1H-pyrrol-2-yl)methane
  参考文献：
  名称：

  Efficient Synthesis of Bis(heterocyclyl)methanes

  摘要：

  The reaction of pyrrole/furan aldehyde with Grignard reagent and pyrrole/N-methyl pyrrole in sequence allows efficient synthesis of a number of meso-elaborated bis(heterocyclyl)methanes, which are otherwise difficult to obtain through a direct aldehyde condensation route.

  DOI：

  10.1080/00397911.2010.518330

文献信息

• Rational or Statistical Routes from 1-Acyldipyrromethanes to <i>meso</i>-Substituted Porphyrins. Distinct Patterns, Multiple Pyridyl Substituents, and Amphipathic Architectures
  作者：Dilek Kiper Dogutan、Marcin Ptaszek、Jonathan S. Lindsey

  DOI：10.1021/jo800588n

  日期：2008.8.1

  New methodology is described for the synthesis of porphyrins bearing four (A4, cis-A2B2, cis-ABC2, trans-A2B2) or fewer (A, cis-AB, cis-A2, trans-A2) meso substituents. The method entails condensation of two 1-acyldipyrromethanes in the presence of a metal salt (MgBr2, 3 mol equiv) and a noncoordinating base (DBU, 10 mol equiv) in a noncoordinating solvent (toluene) with heating (conventional or microwave

  描述了一种新的合成方法，用于合成带有四个（A 4，顺式-A 2 B 2，顺式-ABC 2，反式-A 2 B 2）或更少（A，顺式-AB，顺式-A 2，反式- A 2）内消旋取代基。该方法需要在金属盐（MgBr 2，3摩尔当量）和非配位碱（DBU，10摩尔当量）在非配位溶剂（甲苯）中加热（常规或微波辐射）并暴露于空气中。反式-A 2 B 2-或反式-A 2-卟啉的合理合成是通过两个相同的1-酰基二吡咯甲烷的缩合反应实现的。各种内消旋的统计综合通过两个不相同的1-酰基吡咯烷甲烷的缩合获得取代的卟啉。两种途径都具有吸引人的特征，包括（1）无加扰；（2）高浓度（100 mM）的大环形成步骤中的高收率（最高60％）；（3）合理的范围（芳基，杂芳基，烷基或无取代基），（4）微波辐射反应时间短（〜2 h），（5）容易进行脱金属的卟啉镁产物和（6）色谱纯化简便。统计途径的主要优点是获得了顺式取代的卟啉，而没有相应的反式异构体。例如，A
• <i>D</i>_3<i>h</i>-Symmetric Porphyrin-Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One-Nanometer-Sized Cavity
  作者：Yohei Ohkoda、Akane Asaishi、Tomoya Namiki、Tomoaki Hashimoto、Midori Yamada、Koichiro Shirai、Yuta Katagami、Tomoaki Sugaya、Makoto Tadokoro、Akiharu Satake

  DOI：10.1002/chem.201501854

  日期：2015.8.10

  The one‐step synthesis of D3h‐symmetric cyclic porphyrin trimers 1 composed of three 2,2′‐[4,4′‐bis(methoxycarbonyl)]bipyridyl moieties and three porphyrinatozinc moieties was achieved from a nickel‐mediated reductive coupling of meso‐5,15‐bis(6‐chloro‐4‐methoxycarbonylpyrid‐2‐yl)porphyrinatozinc. Although cyclic trimers 1 were obtained as a mixture that included other cyclic and acyclic porphyrin

  D 3 h对称的环状卟啉三聚体1的一步合成是通过镍介导的还原偶合反应实现的，该化合物由三个2,2'-[4,4'-双（甲氧羰基）]联吡啶基和三个卟啉tozinc部分组成。中观-5,15-双（6-氯-4-甲氧基羰基吡啶-2-基）卟啉锌。虽然环状三聚物1被作为包括了其他环状和无环的卟啉低聚物的混合物而获得，仅观察到对环状三聚物的非常具体的分离1使用具有pyrenylethyl，氰基和其它基团改性的硅胶的柱时。循环三聚体的结构分析1借助NMR光谱学和X射线晶体学进行。一个η的治疗3 π-烯丙基配合物与环状三聚体，得到含有三个η三（钯）络合物3的空间中，这表明环内的联吡啶基部分可以作为双齿metalloligands工作内部π-烯丙基基团。
• Dicationic pyridium porphyrins appending different peripheral substituents: Synthesis and studies for their interactions with DNA
  作者：Song Wu、Zheng Li、Lige Ren、Bo Chen、Feng Liang、Xiang Zhou、Tao Jia、Xiaoping Cao

  DOI：10.1016/j.bmc.2005.12.011

  日期：2006.5

  Twelve trans-dicationic pyridium porphyrins appending different peripheral substituents were synthesized and their abilities to bind and cleave DNA under irradiation have been investigated. Their binding modes to DNA were studied by UV-vis spectroscopy, circular dichroism. The apparent constants were measured by EB competitive fluorescence method and most of them were in the range of 10(4) - 10(5) M-1. We found that both the position of positive charges and steric hindrance Could greatly influence their binding affinities and modes to DNA, and then affect their photocleaving abilities to DNA. (c) 2005 Elsevier Ltd. All rights reserved.
• Synthesis and Characterization of Porphyrin-Sugar Carbon Conjugates
  作者：Giovanni Casiraghi、Mara Cornia、Franca Zanardi、Gloria Rassu、Enzio Ragg、Rita Bortolini

  DOI：10.1021/jo00086a035

  日期：1994.4

  The synthesis, structures, and spectroscopic properties of some 5,15-di-C-glycosyl-10,20-diarylporphyrins, representatives of a novel class of meso-C-glycoconjugated porphyrins, have been investigated. Porphyrins 9-14 were prepared in 6-16 % yield by condensation of suitable dipyrrylglycosides with aryl aldehydes in the presence of either trifluoroacetic acid or BF3 promoters. In all instances, alpha,beta-configured porphyrins were preferentially formed, alpha,alpha isomers being only marginal products. The UV-vis spectra in CHCl3 solution showed Soret bands which are red-shifted by about 20 nm as compared to the corresponding absorption maximum of the planar reference compound meso-5,15-bis(p-fluorophenyl)-10,20-diethylporphyrin (15). This suggested that the porphyrin macrocycles of 9-14 are inherently distorted to a significant extent. Detailed 1D and 2D H-1 NMR spectroscopic studies, including variable-temperature experiments in deuterated chloroform or tetrachloroethane, were carried out using the trans-disposed porphyrins 9 and 10. It was found that, at ambient temperature, these porphyrins adopted distorted saddle conformations in solution. Molecular mechanics techniques were used to analyze the distortion of porphyrin 9 as determined by the orientation of carbohydrate legs on the porphyrin periphery.
• Investigation of the Scope of a New Route to ABCD-Bilanes and ABCD-Porphyrins
  作者：Dilek Kiper Dogutan、Jonathan S. Lindsey

  DOI：10.1021/jo8010396

  日期：2008.9.1

  A new route to bilanes and porphyrins bearing four distinct meso substituents has been studied to elucidate the scope and gain entry to previously inaccessible compounds. The route entails (i) synthesis of a 1-bromo-19-acylbilane by acid-catalyzed condensation of a 1-acyldipyrromethane and a 9-bromodipyrromethane-1-carbinol and (ii) intramolecular cyclization of the 1-bromo-19-acylbilane in the presence of a metal salt (MgBr2, 3 mol equiv) and a non-nucleophilic base (DBU, 10 mol equiv) in a noncoordinating solvent (toluene) at 115 degrees C exposed to air to afford the corresponding magnesium(II) porphyrin. In this study, two sets of bilanes were initially prepared to explore substituent effects. In the first set, all bilanes vary only in the nature of the substituent at the 10-position. In the second set, all bilanes vary only in the nature of the substituent attached to the acyl unit (the 20-position). The substituents examined at the 10- and 20-positions include alkyl, aryl (electron-rich, electron-deficient, hindered), heteroaryl, ester, or no substituent (-H). The bilanes were obtained in 35-87% yield, and the target porphyrins in up to 60% yield. Further study of the scope focused on bilanes and porphyrins bearing three heterocyclic substituents (o-, m-, p-pyridyl) or four alkyl groups (ethyl, propyl, butyl, pentyl), in which case microwave irradiation was used for the porphyrin-forming step. Altogether, 17 bilanes and 19 porphyrins were prepared and characterized. In summary, the new route provides access to meso-substituted bilanes and porphyrins for which access is limited via other methods.