2,5-bis(hydroxymethyl)-1-phenyl-1-thiophosphole | 906008-08-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,5-bis(hydroxymethyl)-1-phenyl-1-thiophosphole
• 英文别名: [3-(hydroxymethyl)-2-phenyl-2-sulfanylidene-5,6-dihydro-4H-cyclopenta[c]phosphol-1-yl]methanol
• CAS: 906008-08-0
• 化学式: C₁₅H₁₇O₂PS
• 分子量: 292.339
• InChiKey: YRZFPCYXWYDIGA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  72.6
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,5-bis(hydroxymethyl)-1-phenyl-1-thiophosphole 在 三氟化硼乙醚 、 三(二甲胺基)膦 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 26.0h， 生成
  参考文献：
  名称：

  Synthesis of a Phosphorus-Containing Hybrid Porphyrin

  摘要：

  A phosphorus-containing hybrid porphyrin was successfully prepared via the BF3-promoted dehydrative condensation between sigma(4)-phosphatripyrrane and 2,5-bis[hydroxy(phenyl)methyl]thiophene. The NMR and UV-vis absorption spectra, electrochemical measurements, and DFT calculations revealed that the sigma(3)-P,N-2,S-hybrid porphyrin exhibits high aromaticity as an 18 pi-electron system in terms of both geometric and magnetic criteria.

  DOI：

  10.1021/ol0622763
• 作为产物：
  描述：

  diethyl 2-phenyl-5,6-dihydro-4H-cyclopenta[c]phosphole-1,3-dicarboxylate 在 二异丁基氢化铝 、 1,2,3,4,5,6,7,8-八硫杂环辛烷 作用下， 以 正己烷 为溶剂， 反应 1.0h， 以63%的产率得到2,5-bis(hydroxymethyl)-1-phenyl-1-thiophosphole
  参考文献：
  名称：

  A Convenient Method for the Synthesis of 2,5-Difunctionalized Phospholes Bearing Ester Groups

  摘要：

  Symmetrically and unsymmetrically 2,5-difunctionalized phospholes bearing ester groups were prepared in a one-pot procedure from the corresponding diynes and dichloro-(phenyl) phosphine via titanacyclopentadienes. The observed optical properties of the functionalized phospholes show that the pi-conjugative push-pull interaction between the 2- and 5-substituents plays an important role in controlling the light-emitting efficiency.

  DOI：

  10.1021/jo0605748

文献信息

• Synthesis and Reactions of Phosphaporphyrins: Reconstruction of π-Skeleton Triggered by Oxygenation of a Core Phosphorus Atom
  作者：Takashi Nakabuchi、Makoto Nakashima、Shinya Fujishige、Haruyuki Nakano、Yoshihiro Matano、Hiroshi Imahori

  DOI：10.1021/jo902060b

  日期：2010.1.15

  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.