tetraphenylporphyrinogen | 27226-54-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 英文名称: tetraphenylporphyrinogen
• 英文别名: meso-Tetraphenylporphyrinogen；5,10,15,20-tetraphenyl-porphyrinogen；5,10,15,20-Tetraphenyl-5,10,15,20,21,22,23,24-octahydroporphyrin
• CAS: 27226-54-6
• 化学式: C₄₄H₃₆N₄
• 分子量: 620.797
• InChiKey: JGASYZAOYXKYTC-UHFFFAOYSA-N

物化性质

• 密度：
  1.236±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.9
• 重原子数：
  48
• 可旋转键数：
  4
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  63.2
• 氢给体数：
  4
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  tetraphenylporphyrinogen 在 air 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 生成 tetraphenylporphyrin
  参考文献：
  名称：

  五氯化磷（PCl 5）介导的四芳基卟啉的合成

  摘要：

  描述了用PCl 5作为催化剂由吡咯和取代的苯甲醛合成卟啉的新方法。在这种催化剂的存在下，芳香醛与吡咯不可逆地冷凝，卟啉原的需氧氧化可提供功能化的卟啉，产率为20-65％。

  DOI：

  10.1002/hlca.200390041
• 作为产物：
  描述：

  N-亚苄基-4-甲基苯磺酰胺 、 5-苯基联吡咯甲烷 在 copper(II) bis(trifluoromethanesulfonate) 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 tetraphenylporphyrinogen
  参考文献：
  名称：

  Synthesis of meso-tetraphenyl porphyrins via condensation of dipyrromethanes with N-tosyl imines

  摘要：

  A new synthetic route for the synthesis of 5,10,15,20-tetraphenyl porphyrins has been developed based on the reaction of 5-substituted dipyrromethanes with N-tosyl imines in the presence of a metal triflate catalyst. meso-Substituted tetraphenyl porphyrins were synthesized in a two-step process. The first step of the method is the metal triflate-catalyzed condensation of 5-substituted dipyrromethanes with N-tosyl imines to form a porphyrinogen intermediate and the second step is the oxidation of the porphyrinogen to porphyrin. The method was applied to the synthesis of trans-A(2)B(2)-tetraarylporphyrins and the products were obtained with only a trace amount of one scrambling product. The synthesis of two important building blocks for porphyrin synthesis, mono and di-sulfonamide alkylated 5-substituted dipyrromethanes, was achieved by the addition of 5-substituted dipyrromethane to N-tosyl imine. The application of mono and di-sulfonamide alkylated 5-substituted dipyrromethanes in '2+2' porphyrin formation reactions is presented. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2009.01.009

文献信息

• Cellulose sulfuric acid as a biodegradable and recoverable solid acid catalyst for one pot synthesis of substituted pyrroles under solvent-free conditions at room temperature
  作者：Ali Rahmatpour

  DOI：10.1016/j.reactfunctpolym.2010.11.001

  日期：2011.1

  A new and efficient method for the preparation of N-substituted pyrroles from one-pot condensation reaction of 2,5-hexandione with amines and diamines in the presence of cellulose sulfuric acid (CSA) as a bio-supported catalyst at room temperature under solvent-free conditions is presented. This new protocol has the advantages of easy availability, stability, reusability and eco-friendly of the catalyst

  一种新型高效的方法，在室温下，在溶剂硫酸纤维素（CSA）存在下，由2,5-己二酮与胺和二胺一锅缩合反应制备N-取代的吡咯无条件。该新方案的优点是催化剂容易获得，稳定，可重复使用且对环境友好，产率高至优异，实验和后处理程序简单。
• Effects of methoxy-substituted metalloporphyrins in catalytic alkene epoxidation by n-<font>Bu</font>₄<font>NHSO</font>₅
  作者：Amineh Aghabali、Nasser Safari

  DOI：10.1142/s1088424610002136

  日期：2010.4

  TPPMnOAc and four different kinds of manganese tetraphenylporphyrin acetates were synthesized using different numbers of methoxy substituents in various positions of the phenyl rings. These porphyrins were used as catalysts in the epoxidation of various alkenes with tetra-n-butylammonium hydrogen monopersulfate (n- Bu ₄ NHSO ₅) as the oxidant and imidazole as the axial base. The following order of catalytic activity was obtained: TPPMnOAc ≥ T (2,3- OMeP ) PMnOAc > T (4- OMeP ) PMnOAc > T (3,4- OMeP ) PMnOAc > T (2,4,6- OMeP ) PMnOAc . By studying the UV-vis spectra in the reaction solution, the stability of the applied methoxy porphyrins and the effect of this factor on obtained yields were investigated. Lower catalytic activity in some of the methoxy porphyrins emphasized steric effects and special hydrogen bonding among the reaction elements. However, the stability of T (2,3- OMeP ) PMnOAc under our reaction condition was considerable and high activity was observed. By adding small amounts of alcohol to the reaction solution, the effect of the solvent mixture was previewed and steps were taken to identify the active intermediate of the catalyst in these conditions.

  利用苯环不同位置上不同数量的甲氧基取代基合成了 TPPMnOAc 和四种不同的四苯基卟啉醋酸锰。这些卟啉被用作催化剂，以四正丁基硫酸氢铵（n- Bu 4 NHSO 5）为氧化剂，咪唑为轴向碱，对各种烯烃进行环氧化反应。催化活性顺序如下TPPMnOAc ≥ T (2,3- OMeP ) PMnOAc > T (4- OMeP ) PMnOAc > T (3,4- OMeP ) PMnOAc > T (2,4,6- OMeP ) PMnOAc 。通过研究反应溶液中的紫外-可见光谱，研究了所应用的甲氧基卟啉的稳定性以及该因素对所得产率的影响。一些甲氧基卟啉的催化活性较低，强调了立体效应和反应元素之间特殊的氢键。然而，在我们的反应条件下，T (2,3- OMeP ) PMnOAc 具有很高的稳定性和活性。通过在反应溶液中加入少量的酒精，预览了混合溶剂的影响，并采取步骤确定了催化剂在这些条件下的活性中间体。
• Phosphorus Pentachloride (PCl5) Mediated Synthesis of Tetraarylporphyrins
  作者：Hashem Sharghi、Alireza Hassani Nejad

  DOI：10.1002/hlca.200390041

  日期：2003.2

  A new synthesis of porphyrins from pyrrole and substituted benzaldehydes is described, with PCl5 as catalyst. Aromatic aldehydes condense irreversibly with pyrrole in the presence of this catalyst, and aerobic oxidation of porphyrinogen provides functionalized porphyrins in yields of 20–65%.

  描述了用PCl 5作为催化剂由吡咯和取代的苯甲醛合成卟啉的新方法。在这种催化剂的存在下，芳香醛与吡咯不可逆地冷凝，卟啉原的需氧氧化可提供功能化的卟啉，产率为20-65％。
• Porphyrin synthesis using mechanochemistry: Sustainability assessment
  作者：Carla Gomes、Mariana Peixoto、Marta Pineiro

  DOI：10.1142/s1088424619500755

  日期：2019.7

  Looking for sustainable synthetic methodologies, mechanochemistry as a new tool for one-step and two-step approaches for the synthesis of meso-substituted porphyrins was explored. The best results were obtained in a two-step procedure, under liquid-assisted grinding in the oxidation step using 2-methyltetrahydrofuran, an environmentally acceptable solvent, and MnO₂ as a heterogeneous oxidant. The sustainability was assessed using two sustainability metrics, E-factor and EcoScale, which allow comparison between procedures and methods.

  为了寻找可持续的合成方法，研究人员探索了机械化学作为一步法和两步法合成中取代卟啉的新工具。在两步法中，使用环境可接受的溶剂 2-甲基四氢呋喃和作为异相氧化剂的二氧化锰在氧化步骤中进行液体辅助研磨，获得了最佳结果。可持续发展性的评估采用了两个可持续发展指标，即 E 因子和 EcoScale，这两个指标允许对不同的程序和方法进行比较。
• MnO2 instead of quinones as selective oxidant of tetrapyrrolic macrocycles
  作者：Bruno F.O. Nascimento、António M.d’A. Rocha Gonsalves、Marta Pineiro

  DOI：10.1016/j.inoche.2009.12.032

  日期：2010.3

  Abstract Porphyrins and chlorins were generated through dehydrogenation of the corresponding porphyrinogen and bacteriochlorin precursors using activated manganese dioxide and focused microwave irradiation. The application of this inexpensive heterogeneous oxidant under microwave heating conditions, instead of the quinones usually employed in conventional methodologies, allowed short reaction times

  摘要 卟啉和二氢卟酚是通过使用活化的二氧化锰和聚焦微波辐射使相应的卟啉原和菌绿素前体脱氢而产生的。这种廉价的多相氧化剂在微波加热条件下的应用，而不是传统方法中通常使用的醌类，可以缩短反应时间、简单的整体后处理和良好的产率。