[anti-dispiro[2H-acenaphthylen-1-one-2,5'-10',20'-dimesityldihydroporphyrinato-15',2''-2''H-acenaphthylen-1''-one]] copper

• 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: [anti-dispiro[2H-acenaphthylen-1-one-2,5'-10',20'-dimesityldihydroporphyrinato-15',2''-2''H-acenaphthylen-1''-one]] copper
• 化学式: C₆₀H₄₂N₄O₂*Cu
• 分子量: 914.565
• InChiKey: YMKFWXWFACUHSC-MTYYCPSQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.97
• 重原子数：
  67
• 可旋转键数：
  2
• 环数：
  13.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  60.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  [anti-dispiro[2H-acenaphthylen-1-one-2,5'-10',20'-dimesityldihydroporphyrinato-15',2''-2''H-acenaphthylen-1''-one]] copper 在 氢氧化钾 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以61%的产率得到[α,β-5,15-bis(8-carboxy-1-naphthyl)-10,20-dimesitylporphyrinato]copper dipotassium salt
  参考文献：
  名称：

  New Methodologies for the Preparation of Porphodimethenes and Their Conversion to trans-Porphyrins with Functionalized Naphthyl Spacers

  摘要：

  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.

  DOI：

  10.1021/jo010163l
• 作为产物：
  描述：

  anti-dispiro[2H-acenaphthylen-1-one-2,5'-10',20'-dimesityldihydroporphyrin-15',2'',2''H-acenaphthylen-1''-one] 在 copper diacetate 作用下， 以 甲醇 、 氯仿 为溶剂， 反应 1.0h， 生成 [anti-dispiro[2H-acenaphthylen-1-one-2,5'-10',20'-dimesityldihydroporphyrinato-15',2''-2''H-acenaphthylen-1''-one]] copper
  参考文献：
  名称：

  二螺-卟啉二甲易于氧化成非平面和片状卟啉的氧化重排，在近红外区域具有强吸收。

  摘要：

  DOI：

  10.1002/anie.200352762

文献信息

• Facile Oxidative Rearrangement of Dispiro-Porphodimethenes to Nonplanar and Sheetlike Porphyrins with Intense Absorptions in the Near-IR Region
  作者：Hubert S. Gill、Michael Harmjanz、Javier Santamaría、Isaac Finger、Michael J. Scott

  DOI：10.1002/anie.200352762

  日期：2004.1.16
• 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.