| 1203576-41-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• CAS: 1203576-41-3
• 化学式: C₁₇H₁₈N₂S
• 分子量: 282.409
• InChiKey: ADDHWNVCDDZCNG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.07
• 重原子数：
  20.0
• 可旋转键数：
  4.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  31.58
• 氢给体数：
  2.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  2,5-bis(α-hydroxy-α-phenylmethyl)thiophene 、 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88 mg的产率得到
  参考文献：
  名称：

  Synthesis and Reactions of Phosphaporphyrins: Reconstruction of π-Skeleton Triggered by Oxygenation of a Core Phosphorus Atom

  摘要：

  The synthesis, structures, optical and redox properties, and reactivity of phosphaporphyrins are reported. The 21-phosphaporphyrin (P,N-3-porphyrin) and 23-phospha-21-thiaporphyrin (P,S, N-2-porphyrin) were prepared via acid-promoted dehydrative condensation between a phosphatri-pyrrane and the corresponding 2,5-bis[hydroxy(phenyl)methyl]heteroles followed by 2,3-dichloro-5,6-dicyanobenzoquinone oxidation. Experimental (NMR, UV-vis, and X-ray analyses) and theoretical (DFT calculations) results suggest that the 18 pi aromaticity inherent in regular N-4-porphyrins was maintained in these phosphaporphyrins. X-ray crystallography revealed a slightly distorted 18 pi aromatic ring for the P,N-3-porphyrin with the phosphole and three pyrrole rings tilted from the 24-atoms mean plane by 9.6 degrees and 3.8-15.4 degrees, respectively. DFT calculations on model compounds showed that the P,X,N-2-porphyrins (X = N, S) possess considerably small HOMO-LUMO gaps as compared with N-4- and S,N-3-porphyrins, which is reflected in the red-shifted absorptions, low oxidation potentials, and high reduction potentials of the phosphaporphyrins. The P-oxygenation of the P,X,N-2-porphyrins with H2O2 has been found to lead to the formation of different types of products. The 18 pi, P,N-3-porphyrin was transformed into the 22 pi aromatic P(O), N-3-porphyrin accompanied by the T extension at the peripheral C-3 bridge, whereas the 18 pi P,S,N-2-porphyrin was converted to the isophlorin-type 20 pi antiaromatic P(O),S,N-2-porphyrin. In both of the reactions, simple P-oxygenated 18 pi P(O),X,N-2-porphyrins were formed as the initial products, which were subsequently transformed into the 22 pi or 20 pi porphyrins. The two reaction courses from 18 pi to 20 pi/22 pi are apparently determined by the combination of the core heteroatoms (i.e., P,N-3 or P,S,N-2) and the structure of the peripherally fused carbocycles. The present results demonstrate that the incorporation of a phosphorus atom into the core is not only a highly promising way to modify the fundamental properties of the porphyrin 18 pi system but also a reliable tool to stabilize uncommon 22 pi and 20 pi systems through the chemical modifications at the core phosphorus atom.

  DOI：

  10.1021/jo902060b
• 作为产物：
  描述：

  吡咯 、 [3-(hydroxymethyl)-5,6-dihydro-4H-cyclopenta[c]thiophen-1-yl]methanol 在 三氟化硼乙醚 作用下， 反应 0.5h， 生成
  参考文献：
  名称：

  Synthesis and Reactions of Phosphaporphyrins: Reconstruction of π-Skeleton Triggered by Oxygenation of a Core Phosphorus Atom

  摘要：

  The synthesis, structures, optical and redox properties, and reactivity of phosphaporphyrins are reported. The 21-phosphaporphyrin (P,N-3-porphyrin) and 23-phospha-21-thiaporphyrin (P,S, N-2-porphyrin) were prepared via acid-promoted dehydrative condensation between a phosphatri-pyrrane and the corresponding 2,5-bis[hydroxy(phenyl)methyl]heteroles followed by 2,3-dichloro-5,6-dicyanobenzoquinone oxidation. Experimental (NMR, UV-vis, and X-ray analyses) and theoretical (DFT calculations) results suggest that the 18 pi aromaticity inherent in regular N-4-porphyrins was maintained in these phosphaporphyrins. X-ray crystallography revealed a slightly distorted 18 pi aromatic ring for the P,N-3-porphyrin with the phosphole and three pyrrole rings tilted from the 24-atoms mean plane by 9.6 degrees and 3.8-15.4 degrees, respectively. DFT calculations on model compounds showed that the P,X,N-2-porphyrins (X = N, S) possess considerably small HOMO-LUMO gaps as compared with N-4- and S,N-3-porphyrins, which is reflected in the red-shifted absorptions, low oxidation potentials, and high reduction potentials of the phosphaporphyrins. The P-oxygenation of the P,X,N-2-porphyrins with H2O2 has been found to lead to the formation of different types of products. The 18 pi, P,N-3-porphyrin was transformed into the 22 pi aromatic P(O), N-3-porphyrin accompanied by the T extension at the peripheral C-3 bridge, whereas the 18 pi P,S,N-2-porphyrin was converted to the isophlorin-type 20 pi antiaromatic P(O),S,N-2-porphyrin. In both of the reactions, simple P-oxygenated 18 pi P(O),X,N-2-porphyrins were formed as the initial products, which were subsequently transformed into the 22 pi or 20 pi porphyrins. The two reaction courses from 18 pi to 20 pi/22 pi are apparently determined by the combination of the core heteroatoms (i.e., P,N-3 or P,S,N-2) and the structure of the peripherally fused carbocycles. The present results demonstrate that the incorporation of a phosphorus atom into the core is not only a highly promising way to modify the fundamental properties of the porphyrin 18 pi system but also a reliable tool to stabilize uncommon 22 pi and 20 pi systems through the chemical modifications at the core phosphorus atom.

  DOI：

  10.1021/jo902060b