Decyl 3-[2-[5-[2-[3-decoxycarbonyl-5-[2-[1,12-dimethyl-5-(2-trimethylsilylethynyl)benzo[c]phenanthren-8-yl]ethynyl]phenyl]ethynyl]-1,12-dimethylbenzo[c]phenanthren-8-yl]ethynyl]-5-[2-[1,12-dimethyl-5-(2-trimethylsilylethynyl)benzo[c]phenanthren-8-yl]ethynyl]benzoate | 803724-24-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: Decyl 3-[2-[5-[2-[3-decoxycarbonyl-5-[2-[1,12-dimethyl-5-(2-trimethylsilylethynyl)benzo[c]phenanthren-8-yl]ethynyl]phenyl]ethynyl]-1,12-dimethylbenzo[c]phenanthren-8-yl]ethynyl]-5-[2-[1,12-dimethyl-5-(2-trimethylsilylethynyl)benzo[c]phenanthren-8-yl]ethynyl]benzoate
• CAS: 803724-24-5
• 化学式: C₁₁₂H₁₀₈O₄Si₂
• 分子量: 1574.26
• InChiKey: ZDJVQHNDUPGJOK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  28.57
• 重原子数：
  118
• 可旋转键数：
  34
• 环数：
  14.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Decyl 3-[2-[5-[2-[3-decoxycarbonyl-5-[2-[1,12-dimethyl-5-(2-trimethylsilylethynyl)benzo[c]phenanthren-8-yl]ethynyl]phenyl]ethynyl]-1,12-dimethylbenzo[c]phenanthren-8-yl]ethynyl]-5-[2-[1,12-dimethyl-5-(2-trimethylsilylethynyl)benzo[c]phenanthren-8-yl]ethynyl]benzoate 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以100%的产率得到C₁₀₆H₉₂O₄
  参考文献：
  名称：

  Synthesis and Self-aggregation of Cyclic Alkynes Containing Helicene

  摘要：

  All stereoisomers of a cyclic alkyne containing three helicene units, 1,12-dimethylbenzo[c]phenanthrene, are synthesized using a building block. Isomeric [3 + 3]cycloalkynes aggregate in organic solvents, Vapor pressure osmometry reveals dimer formation of (M,M,M)-[3 + 3] cycloalkynes in chloroform and benzene at concentrations above 2 mM. No higher aggregation is observed. The chirality of helicenes plays an important role in self aggregation, and diastereomeric (M,P,M)-[3 + 3]cycloalkyne forms a dimer only above 15 mM. Aggregation of racemic (M*,M*,M*)-[3 + 3]cycloalkyne or (M*,P*,M*)-[3 + 3]cycloalkyne is much weaker than that of a single enantiomer.

  DOI：

  10.1021/ol015550w
• 作为产物：
  描述：

  (M)-5,8-diethynyl-1,12-dimethylbenzo[c]phenanthrene 、 decyl (M)-3-[1',12'-dimethyl-8'-(trimethylsilylethynyl)benzo[c]phenanthryl-5'-ethynyl]-5-trifluoromethanesulfoxybenzoate 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 四丁基碘化铵 copper(l) iodide 、 三异丙叉丙酮基膦 、 三苯基膦 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 以83%的产率得到Decyl 3-[2-[5-[2-[3-decoxycarbonyl-5-[2-[1,12-dimethyl-5-(2-trimethylsilylethynyl)benzo[c]phenanthren-8-yl]ethynyl]phenyl]ethynyl]-1,12-dimethylbenzo[c]phenanthren-8-yl]ethynyl]-5-[2-[1,12-dimethyl-5-(2-trimethylsilylethynyl)benzo[c]phenanthren-8-yl]ethynyl]benzoate
  参考文献：
  名称：

  Synthesis and Self-aggregation of Cyclic Alkynes Containing Helicene

  摘要：

  All stereoisomers of a cyclic alkyne containing three helicene units, 1,12-dimethylbenzo[c]phenanthrene, are synthesized using a building block. Isomeric [3 + 3]cycloalkynes aggregate in organic solvents, Vapor pressure osmometry reveals dimer formation of (M,M,M)-[3 + 3] cycloalkynes in chloroform and benzene at concentrations above 2 mM. No higher aggregation is observed. The chirality of helicenes plays an important role in self aggregation, and diastereomeric (M,P,M)-[3 + 3]cycloalkyne forms a dimer only above 15 mM. Aggregation of racemic (M*,M*,M*)-[3 + 3]cycloalkyne or (M*,P*,M*)-[3 + 3]cycloalkyne is much weaker than that of a single enantiomer.

  DOI：

  10.1021/ol015550w

文献信息

• Marked Effect of Aromatic Solvent on Unfolding Rate of Helical Ethynylhelicene Oligomer
  作者：Hiroki Sugiura、Yasuko Nigorikawa、Yuto Saiki、Keiichi Nakamura、Masahiko Yamaguchi

  DOI：10.1021/ja0478882

  日期：2004.11.1

  Optically active acyclic ethynylhelicene oligomers were synthesized in high yields by a two-directional method involving Sonogashira coupling and deprotection. Their CD spectra in chloroform exhibited large differences between the oligomers with less than seven helicenes and their higher homologues, which indicated the formation of helical structures for the latter and random coil structures for the former. The helical heptamer gradually unfolded to a random coil structure in chloroform at room temperature. The unfolding rate was examined by CD in several aromatic solvents as well, and the rate constant k was found to be highly dependent on the type of aromatic substituent: k differed by seven orders of magnitude between iodobenzene and trifluoromethylbenzene. Several features of the rates are notable: The reaction rates in halobenzenes were in the order of iodobenzene > bromobenzene >chlorobenzene > benzene > fluorobenzene > m-difluorobenzene, those in alkylbenzenes were styrene > phenylacetylene > ethylbenzene > toluene > benzene, and those in heteroatom-substituted arenes were thioanisole > benzonitrile > anisole > ethyl benzoate > benzene > trifluoromethylbenzene. The log kvalues exhibited good correlation with the absolute hardness, eta, of the arenes, and higher unfolding rates were observed in the soft arenes. Vapor pressure osmometry studies indicated that the helical structure of the heptamer is dimeric in benzene, fluorobenzene, and trifluoromethylbenzene, while the random coil structure of the heptamer is monomeric in chloroform and toluene. When a chloroform solution of the random coil structure was concentrated to a small volume, the helical structure could be regenerated.