silaphane | 132645-09-1

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: silaphane
• 英文别名: 8,16,29-trithia-1-silahexacyclo[10.10.8.110,14.02,7.017,22.023,28]hentriaconta-2,4,6,10,12,14(31),17,19,21,23,25,27-dodecaene
• CAS: 132645-09-1
• 化学式: C₂₇H₂₂S₃Si
• 分子量: 470.755
• InChiKey: VSNMKMTWXLLMPR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.44
• 重原子数：
  31.0
• 可旋转键数：
  0.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为产物：
  描述：

  Lithium 2-lithiobenzenethiolate 在 氢氧化钾 、 三氯硅烷 作用下， 以 四氢呋喃 、 乙醇 、 苯 为溶剂， 反应 36.0h， 生成 silaphane
  参考文献：
  名称：

  in-Cyclophanes containing second-row elements poised above aromatic rings

  摘要：

  The silicon- and phosphorus-containing cyclophanes 2 and 3 were prepared by base-promoted condensation of tris(2-mercaptophenyl)silane and tris(2-mercaptophenyl)phosphine, respectively, with 1,3,5-tris(bromomethyl)benzene. The structures of both cyclophanes were determined by X-ray crystallography. In compound 2, the distance from the apical silicon to the center of the basal aromatic ring was 3.34 angstrom, and in 3 the corresponding phosphorus to ring distance was 2.90 angstrom. The H-1 NMR spectrum of 2 was characterized by a high-field Si-H resonance (delta-1.04, 5 ppm upfield from the corresponding resonance in an acyclic model), and the IR spectrum showed a high-frequency Si-H stretching band (2457 cm-1, 280 cm-1 above the acyclic model); both features result from the proximity of the in-hydrosilane to the aromatic ring. For cyclophane 3, the C-13 NMR spectrum exhibited ''through-space'' spin-spin coupling of the phosphorus atom with the carbons of the basal aromatic ring (J(PC)(methine) = 7.5 Hz and J(PC)(quaternary) = 3.5 Hz) and in the P-31 NMR spectrum the phosphorus resonance was 32 ppm downfield from that of an acyclic model, both features suggesting an unusual electronic interaction of the phosphine with the base. Due to a strong preference for an in geometry (pyramidalization of the phosphine toward the basal ring) and the consequent steric shielding, the phosphine of 3 was quite unreactive: It was not protonated by anhydrous HBr, and even when 3 was heated in refluxing hydrogen peroxide and acetic acid, the corresponding trisulfone was obtained without formation of the phosphine oxide.

  DOI：

  10.1021/ja00007a047

文献信息

• LESPERANCE, ROBERT P.;WEST, ANTHONY P. (JR);VAN, ENGEN DONNA;PASCAL, ROBE+, J. AMER. CHEM. SOC., 113,(1991) N, C. 2672-2676
  作者：LESPERANCE, ROBERT P.、WEST, ANTHONY P. (JR)、VAN, ENGEN DONNA、PASCAL, ROBE+

  DOI：——

  日期：——
• in-Cyclophanes containing second-row elements poised above aromatic rings
  作者：Robert P. L'Esperance、Anthony P. West、Donna Van Engen、Robert A. Pascal

  DOI：10.1021/ja00007a047

  日期：1991.3

  The silicon- and phosphorus-containing cyclophanes 2 and 3 were prepared by base-promoted condensation of tris(2-mercaptophenyl)silane and tris(2-mercaptophenyl)phosphine, respectively, with 1,3,5-tris(bromomethyl)benzene. The structures of both cyclophanes were determined by X-ray crystallography. In compound 2, the distance from the apical silicon to the center of the basal aromatic ring was 3.34 angstrom, and in 3 the corresponding phosphorus to ring distance was 2.90 angstrom. The H-1 NMR spectrum of 2 was characterized by a high-field Si-H resonance (delta-1.04, 5 ppm upfield from the corresponding resonance in an acyclic model), and the IR spectrum showed a high-frequency Si-H stretching band (2457 cm-1, 280 cm-1 above the acyclic model); both features result from the proximity of the in-hydrosilane to the aromatic ring. For cyclophane 3, the C-13 NMR spectrum exhibited ''through-space'' spin-spin coupling of the phosphorus atom with the carbons of the basal aromatic ring (J(PC)(methine) = 7.5 Hz and J(PC)(quaternary) = 3.5 Hz) and in the P-31 NMR spectrum the phosphorus resonance was 32 ppm downfield from that of an acyclic model, both features suggesting an unusual electronic interaction of the phosphine with the base. Due to a strong preference for an in geometry (pyramidalization of the phosphine toward the basal ring) and the consequent steric shielding, the phosphine of 3 was quite unreactive: It was not protonated by anhydrous HBr, and even when 3 was heated in refluxing hydrogen peroxide and acetic acid, the corresponding trisulfone was obtained without formation of the phosphine oxide.