(1S,6'E,9'Z,15'R,16'E,19'Z)-10',20'-bis(3,5-di-tert-butylphenyl)-2H,2''H-dispiro[acenaphthylene-1,5'-porphyrin-15',1''-acenaphthylene]-2,2''-dione | 360076-32-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (1S,6'E,9'Z,15'R,16'E,19'Z)-10',20'-bis(3,5-di-tert-butylphenyl)-2H,2''H-dispiro[acenaphthylene-1,5'-porphyrin-15',1''-acenaphthylene]-2,2''-dione
• CAS: 360076-32-0
• 化学式: C₇₀H₆₄N₄O₂
• 分子量: 993.304
• InChiKey: GDQTVLPHOSSSEE-SZJCNVTBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  16.06
• 重原子数：
  76.0
• 可旋转键数：
  2.0
• 环数：
  13.0
• sp3杂化的碳原子比例：
  0.26
• 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：

  (1S,6'E,9'Z,15'R,16'E,19'Z)-10',20'-bis(3,5-di-tert-butylphenyl)-2H,2''H-dispiro[acenaphthylene-1,5'-porphyrin-15',1''-acenaphthylene]-2,2''-dione 在 氢氧化钾 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以90%的产率得到
  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：

  (3,5-di-tert-butylphenyl)di(pyrrol-2-yl)methane 、 苊醌 在 三氟乙酸 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 4.0h， 以12%的产率得到(1S,6'E,9'Z,15'R,16'E,19'Z)-10',20'-bis(3,5-di-tert-butylphenyl)-2H,2''H-dispiro[acenaphthylene-1,5'-porphyrin-15',1''-acenaphthylene]-2,2''-dione
  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