11-nitro-8,16,29-trithia-1-phosphahexacyclo[10.10.8.110,14.02,7.017,22.023,28]hentriaconta-2,4,6,10(31),11,13,17,19,21,23,25,27-dodecaene | 149036-69-1

• 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: 11-nitro-8,16,29-trithia-1-phosphahexacyclo[10.10.8.110,14.02,7.017,22.023,28]hentriaconta-2,4,6,10(31),11,13,17,19,21,23,25,27-dodecaene
• CAS: 149036-69-1
• 化学式: C₂₇H₂₀NO₂PS₃
• 分子量: 517.633
• InChiKey: WJOSGRARXJQQAF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.86
• 重原子数：
  34.0
• 可旋转键数：
  1.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  43.14
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  11-nitro-8,16,29-trithia-1-phosphahexacyclo[10.10.8.110,14.02,7.017,22.023,28]hentriaconta-2,4,6,10(31),11,13,17,19,21,23,25,27-dodecaene 在 titanium(III) chloride 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 0.1h， 以79%的产率得到8,16,29-trithia-1-phosphahexacyclo[10.10.8.110,14.02,7.017,22.023,28]hentriaconta-2,4,6,10(31),11,13,17,19,21,23,25,27-dodecaen-11-amine
  参考文献：
  名称：

  Synthesis, molecular structure, and properties of in-phosphaphanes with substituted basal aromatic rings

  摘要：

  A series of nitro-substituted phosphine-containing cyclophanes (2-4) was prepared by base-promoted condensation of various nitrated derivatives of 1,3,5-tris(bromomethyl)benzene with tris(2-mercaptophenyl)phosphine under conditions of high dilution. The mononitro cyclophane 2 was reduced with TiCl3 in THF-EtOH to give the corresponding amino derivative 5. The C-13 NMR spectra of these compounds exhibit ''through-space'' spin-spin coupling between the phosphorus and the substituted basal aromatic ring, and in their P-31 NMR spectra the phosphorus resonances are anomalously far downfield. The nitro-substituted phanes are colored, probably due to charge-transfer absorptions between the phosphine and the nitroarene base. The X-ray crystal structures of cyclophanes 4 and 5 reveal a pronounced inward pyramidalization of the phosphines such that the phosphorus atoms are 2.98 and 2.92 angstrom, respectively, from the centers of the basal rings. These cyclophanes are rigid, molecular propellers, and compound 2 was chromatographically resolved on a chiral HPLC column. The circular dichroism spectra of the pure enantiomers showed a very high molecular ellipticity at 332 nm of 120 000 deg.cm2.dmol-1.

  DOI：

  10.1021/jo00065a009
• 作为产物：
  描述：

  1,3,5-三(溴甲基)苯 在 氢氧化钾 、 硫酸 、 硝酸 作用下， 以 乙醇 、 苯 为溶剂， 反应 12.0h， 生成 11-nitro-8,16,29-trithia-1-phosphahexacyclo[10.10.8.110,14.02,7.017,22.023,28]hentriaconta-2,4,6,10(31),11,13,17,19,21,23,25,27-dodecaene
  参考文献：
  名称：

  Synthesis, molecular structure, and properties of in-phosphaphanes with substituted basal aromatic rings

  摘要：

  A series of nitro-substituted phosphine-containing cyclophanes (2-4) was prepared by base-promoted condensation of various nitrated derivatives of 1,3,5-tris(bromomethyl)benzene with tris(2-mercaptophenyl)phosphine under conditions of high dilution. The mononitro cyclophane 2 was reduced with TiCl3 in THF-EtOH to give the corresponding amino derivative 5. The C-13 NMR spectra of these compounds exhibit ''through-space'' spin-spin coupling between the phosphorus and the substituted basal aromatic ring, and in their P-31 NMR spectra the phosphorus resonances are anomalously far downfield. The nitro-substituted phanes are colored, probably due to charge-transfer absorptions between the phosphine and the nitroarene base. The X-ray crystal structures of cyclophanes 4 and 5 reveal a pronounced inward pyramidalization of the phosphines such that the phosphorus atoms are 2.98 and 2.92 angstrom, respectively, from the centers of the basal rings. These cyclophanes are rigid, molecular propellers, and compound 2 was chromatographically resolved on a chiral HPLC column. The circular dichroism spectra of the pure enantiomers showed a very high molecular ellipticity at 332 nm of 120 000 deg.cm2.dmol-1.

  DOI：

  10.1021/jo00065a009