(5,15-bis(3-methoxyphenyl)porphyrinato)nickel(II) | 796883-58-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: (5,15-bis(3-methoxyphenyl)porphyrinato)nickel(II)
• CAS: 796883-58-4
• 化学式: C₃₄H₂₄N₄NiO₂
• 分子量: 579.28
• InChiKey: MHWODUUCCCAGGC-MFARDAESSA-N

物化性质

• 熔点：
  340 °C

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (5,15-bis(3-methoxyphenyl)porphyrinato)nickel(II) 在 硫酸 、 三氟乙酸 、 三氯氧磷 作用下， 以 二氯甲烷 为溶剂， 反应 15.5h， 生成 5-formyl-10,20-di(3-methoxyphenyl)porphyrin
  参考文献：
  名称：

  Synthesis and characterization of novel 5-monocarbohydrate-10,20-bis-aryl-porphyrins

  摘要：

  通过标准光谱技术，开发并鉴定了含有葡萄糖或半乳糖单元的衍生物的合成方法，这些单元通过丙烯酸酯间隔物连接到双芳基卟啉大环的一个自由介位上。新的单取代葡萄糖卟啉和半乳糖卟啉衍生物 5-8 是四芳基卟啉广泛官能化的替代品。单线态氧研究表明，其产生的单线态氧与 TPP 相当。此外，这里合成的不太笨重的结构提供了一个机会，只需在其中一个中间位置进行简单的合成修饰，就能增强糖卟啉的光致发射效应和光致分辨能力。

  DOI：

  10.1142/s1088424619501049
• 作为产物：
  描述：

  2,2'-二吡咯基甲烷 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 、 N,N-二甲基甲酰胺 为溶剂， 反应 9.5h， 生成 (5,15-bis(3-methoxyphenyl)porphyrinato)nickel(II)
  参考文献：
  名称：

  Synthesis and characterization of novel 5-monocarbohydrate-10,20-bis-aryl-porphyrins

  摘要：

  通过标准光谱技术，开发并鉴定了含有葡萄糖或半乳糖单元的衍生物的合成方法，这些单元通过丙烯酸酯间隔物连接到双芳基卟啉大环的一个自由介位上。新的单取代葡萄糖卟啉和半乳糖卟啉衍生物 5-8 是四芳基卟啉广泛官能化的替代品。单线态氧研究表明，其产生的单线态氧与 TPP 相当。此外，这里合成的不太笨重的结构提供了一个机会，只需在其中一个中间位置进行简单的合成修饰，就能增强糖卟啉的光致发射效应和光致分辨能力。

  DOI：

  10.1142/s1088424619501049

文献信息

• One-Pot Synthesis of <i>meso</i>-Formylporphyrins by S_NAr Reaction of 5,15-Disubstituted Porphyrins with (2-Pyridyldimethylsilyl)methyllithium
  作者：Toshikatsu Takanami、Atsushi Wakita、Aoyo Sawaizumi、Kazuhiro Iso、Hidetoshi Onodera、Kohji Suda

  DOI：10.1021/ol703107t

  日期：2008.2.1

  A simple, one-pot procedure that converts 5,15-substituted porphyrins into the corresponding meso-formylated porphyrins has been developed. The method, based on a new synthetic concept for functionalized porphyrins utilizing the (2-pyridyldimethylsilyl)methyl group as a latent formyl functionality, affords the desired product in good yield and is especially appropriate for the direct formylation of

  已经开发出一种简单的一锅法，该程序可以将5,15-取代的卟啉转化为相应的内消旋甲酰基化的卟啉。该方法基于利用（2-吡啶基二甲基甲硅烷基）甲基作为潜在的甲酰基官能团的官能化卟啉的新合成概念，以良好的收率提供了所需的产物，尤其适用于从未有过的游离碱卟啉的直接甲酰化反应。通过已知方法实现。
• Exploration ofmeso-Substituted Formylporphyrins and Their Grignard and Wittig Reactions
  作者：Katja Dahms、Mathias O. Senge、M. Bakri Bakar

  DOI：10.1002/ejoc.200700380

  日期：2007.8

  porphyrin spirobisdithanyl-linked bioconjugates. The obtained formylporphyrins were reacted with organomagnesium or organophosphorus compounds. A series of hydroxyporphyrins resulting from the Grignard reaction of 5,15-substituted porphyrins were synthesised in high yields. Several porphyrins with unsaturated residues introduced by the Wittig reaction were obtained in moderate yields. The less sterically hindered

  甲酰基卟啉是通过使用 1,3-二噻吩-2-基残基作为 CHO 基团的前体或通过 Vilsmeier 反应制备的。探索了引入 1,2-dithian-2-yl 基团的两种合成路线。此外，研究了 1,3,5-trithian-2-yl 基团与卟啉的反应，以及作为前体的螺二二噻烷衍生物，用于最终组装卟啉螺双二噻吩连接的生物共轭物。得到的甲酰基卟啉与有机镁或有机磷化合物反应。以高产率合成了一系列由 5,15-取代卟啉的格氏反应产生的羟基卟啉。通过 Wittig 反应引入了几种具有不饱和残基的卟啉，收率适中。空间位阻越小 5，15-取代的卟啉表现出更高的反应性和更高的产率；与其他卟啉系统相比，它们的反应产物稳定性更高。 (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
• Lead structures for applications in photodynamic therapy. Part 1: Synthesis and variation of m-THPC (Temoporfin) related amphiphilic A2BC-type porphyrins
  作者：Arno Wiehe、Yasser M. Shaker、Johan C. Brandt、Stefan Mebs、Mathias O. Senge

  DOI：10.1016/j.tet.2005.03.086

  日期：2005.6

  Photodynamic therapy (PDT) is a developing modality for the treatment of certain tumorous and other diseases. Considerable progress has been made in recent years in the search for new photosensitizers, in particular elucidating the role of localization of the photosensitizer. Known successful photosensitizers of the tetrapyrrole type are amphiphilic molecules, preferably localizing in cellular membrane structures. Thus, the quest for new photosensitizers requires the synthesis of unsymmetrically Substituted (amphiphilic) tetrapyrroles. In this article. we describe strategies for the de novo synthesis of amphiphilic tetrapyrroles using a 3-hydroxyphenyl substituted tetrapyrrolic system (Temoporfin) as the lead structure. From an applied science-oriented approach, such a set of amphiphilic porphyrins is best synthesized by combining well-developed condensation methods with subsequent functionalization via organolithium compound or transition metal catalyzed coupling protocols. Starting from simple A(2)- or AB-porphyrins, the synthesis of A(2)B-, A(3)-, A(3)B-, and A(2)BC-porphyrins with a mixed hydrophilic/hydrophobic substitution pattern is described. Because of the versatility of this approach to unsymmetrically Substituted porphyrins it is also applicable to other areas where porphyryns with a tailor-made substitution patterns are needed. for example. catalysts or molecular electronic devices based on tetrapyrroles. (c) 2005 Elsevier Ltd. All rights reserved.
• The Dithianyl Group as a Synthon in Porphyrin Chemistry:  Condensation Reactions and Preparation of Formylporphyrins under Basic Conditions
  作者：Mathias O. Senge、Sabine S. Hatscher、Arno Wiehe、Katja Dahms、Andrea Kelling

  DOI：10.1021/ja045223u

  日期：2004.10.1

  Vilsmeier formylation is one of the most widely used substitution reactions for the functionalization of porphyrins. However, its utility is limited by the electrophilic/acidic reaction conditions, deactivation of the aromatic system and regiochemical problems, the requirement for metal complexes and necessity for subsequent demetalation under harsh conditions, and low functional group tolerance. To overcome these limitations, the dithianyl group has been utilized as a latent formyl synthon in porphyrin chemistry. 2-Formyl-1,3-dithiane can be used directly in pyrrole condensation reactions to regioselectively yield porphyrins with up to four dithianyl residues. Likewise, 5-dithianyldipyrromethane could be prepared quantitatively as a key building block for various porphyrin condensation reactions yielding the respective free base formylporphyrins after deprotection. Additionally, dithianyllithium can be used as a reagent for the direct aromatic substitution of metallo- and free base porphyrins under nucleophilic conditions.