syn-dispiro[2H-acenaphthylen-1-one-2,5'-10',20'-dimesityldihydroporphyrin-15',2'',2''H-acenaphthylen-1''-one] | 268728-62-7

• 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: syn-dispiro[2H-acenaphthylen-1-one-2,5'-10',20'-dimesityldihydroporphyrin-15',2'',2''H-acenaphthylen-1''-one]
• CAS: 268728-62-7
• 化学式: C₆₀H₄₄N₄O₂
• 分子量: 853.035
• InChiKey: XTTGGAQHOJSGCI-CNXBOBBLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.72
• 重原子数：
  66.0
• 可旋转键数：
  2.0
• 环数：
  13.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  90.44
• 氢给体数：
  2.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  syn-dispiro[2H-acenaphthylen-1-one-2,5'-10',20'-dimesityldihydroporphyrin-15',2'',2''H-acenaphthylen-1''-one] 在 氢氧化钾 作用下， 以 四氢呋喃 为溶剂， 以92%的产率得到α,α-5,15-bis(8-carboxy-1-naphthyl)-10,20-dimesitylporphyrin
  参考文献：
  名称：

  A convenient synthesis of porphodimethenes and their conversion to trans-porphyrins with two functionalized meso-naphthyl substituents

  摘要：

  现成的 5-甲基二吡咯甲烷与苊醌的麦氏唐纳德式 2 + 2 缩合反应可分别生成反式（同义和反义）多孔二甲酚，在 THF 中用 KOH 或 NaOMe 处理并随后用空气氧化后，可生成相应的反式-8-羧基萘卟啉或其酯。

  DOI：

  10.1039/a907992k
• 作为产物：
  描述：

  2-(二吡咯-2-基)甲基三甲苯 、 苊醌 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， 反应 5.0h， 以18%的产率得到anti-dispiro[2H-acenaphthylen-1-one-2,5'-10',20'-dimesityldihydroporphyrin-15',2'',2''H-acenaphthylen-1''-one]
  参考文献：
  名称：

  A convenient synthesis of porphodimethenes and their conversion to trans-porphyrins with two functionalized meso-naphthyl substituents

  摘要：

  现成的 5-甲基二吡咯甲烷与苊醌的麦氏唐纳德式 2 + 2 缩合反应可分别生成反式（同义和反义）多孔二甲酚，在 THF 中用 KOH 或 NaOMe 处理并随后用空气氧化后，可生成相应的反式-8-羧基萘卟啉或其酯。

  DOI：

  10.1039/a907992k

文献信息

• New Methodologies for the Preparation of Porphodimethenes and Their Conversion to <i>trans</i>-Porphyrins with Functionalized Naphthyl Spacers
  作者：Michael Harmjanz、Hubert S. Gill、Michael J. Scott

  DOI：10.1021/jo010163l

  日期：2001.8.1

  The MacDonald [2 + 2]-type condensation of readily available 5-aryl-substituted dipyrromethanes with acenaphthenequinone leads to the trans-syn- and anti-porphodimethenes, which in turn can be converted to the alpha,alpha- and alpha,beta -porphyrin atropisomers, respectively. Treatment of the metalated or unmetalated porphodimethenes with KOH or NaOMe in THF followed by protonation with HCl results in a ring opening of the acenaphthenone and formation of the trans-8-carboxynaphthylporphyrins or their esters (NaOMe) after oxidation. Alternatively, the porphyrin formation can be accomplished by reaction of the porphodimethenes with acids in the presence of water or methanol. Reaction with NaBH4 in a THF-methanol mixture yields the corresponding dialcohols in nearly quantitative yields. Sixteen different building blocks were prepared in order to evaluate the generality of this new synthetic approach, with Ar = 2,4,6-Me3C6H2; 2,6-Cl2C6H3; 2,6-F2C6H3; 3,4-tBu(2)C(6)H(3); 3,4,5-(MeO)(3)C6H2; 4-BrC6H4; 4-MeC6H4; and 4-MeOOCC6H4 at the meso positions. The synthesized porphodimethenes and porphyrins have been fully characterized, and the X-ray structure analyses of three representative derivatives are presented.