| 796883-56-2

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• CAS: 796883-56-2
• 化学式: C₃₆H₂₆N₄NiS₂
• 分子量: 637.451
• InChiKey: VNIIFFSFNOYOQG-KRNCZASPSA-N

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：

  在 三氟化硼乙醚 、 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96%的产率得到5-formyl-10,20-diphenylporphyrinatonickel(II)
  参考文献：
  名称：

  The Dithianyl Group as a Synthon in Porphyrin Chemistry:  Condensation Reactions and Preparation of Formylporphyrins under Basic Conditions

  摘要：

  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.

  DOI：

  10.1021/ja045223u
• 作为产物：
  描述：

  2-lithio-1,3-dithiane 、 (5,15-diphenylporphyrinato)nickel(II) 在 四甲基乙二胺 、 水 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 四氢呋喃 为溶剂， 以54%的产率得到
  参考文献：
  名称：

  The Dithianyl Group as a Synthon in Porphyrin Chemistry:  Condensation Reactions and Preparation of Formylporphyrins under Basic Conditions

  摘要：

  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.

  DOI：

  10.1021/ja045223u

文献信息

• 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)