Triisopropyl-(3,8,13,18-tetracyclohexylidene-icosa-1,4,6,9,11,14,16,19-octaynyl)-silane | 483370-44-1

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: Triisopropyl-(3,8,13,18-tetracyclohexylidene-icosa-1,4,6,9,11,14,16,19-octaynyl)-silane
• CAS: 483370-44-1
• 化学式: C₅₃H₆₂Si
• 分子量: 727.161
• InChiKey: XUDAVLMUUKLKLA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.9
• 重原子数：
  54.0
• 可旋转键数：
  3.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  Triisopropyl-(3,8,13,18-tetracyclohexylidene-icosa-1,4,6,9,11,14,16,19-octaynyl)-silane 在 Hay catalyst 作用下， 以 二氯甲烷 为溶剂， 反应 17.0h， 以18%的产率得到3,8,13,18,23,38,33,38-octakis(cyclohexylidene)-1,40-bis(triisopropylsilyl)tetraconta-1,4,6,9,11,14,16,19,21,24,26,29,31,34,36,36-hexadecayne
  参考文献：
  名称：

  Synthesis and Characterization of Multinanometer-Sized Expanded Dendralenes with an iso-Poly(triacetylene) Backbone

  摘要：

  A series of [n]dendralenes (n = 3, 4, 8, 3b -d (Fig. 1)) expanded with buta-1,3-diynediyl moieties between the C=C bonds were prepared by repetitive acetylenic scaffolding of 3-(cyclohexylidene)penta-1,4-diyne building blocks (Scheme). These remarkably unstable iso-poly(triacetylene) (iso-PTA) oligomers were characterized by H-1- and C-13-NMR (Fig. 3 and Table 1), IR, and UV/VIS (Figs. 4 and 6 and Table 2) spectroscopy, as well as mass spectrometry (Fig. 2). The expanded [8]dendralene contains 40 C(sp)- and C(sp(2))-atoms in the backbone and represents the longest iso-PTA oligomer prepared to date. HOMO-LUMO Gap energies were determined as a function of oligomeric length (Fig. 5 and Table 3), providing insight into the degree of T-electron delocalization in these cross-conjugated chromophores. A continous drop in the HOMO-LUMO gap with increasing number of monomeric repeating units provides evidence that cross-conjugation along the oligomeric backbone is effective to some extent. The limiting HOMO-LUMO gap energy for an infinitely long, buta-1,3-diynediyl-expanded dendralene was extrapolated to about 3.3 - 3.5 eV. The conformational preferences of the expanded dendralenes were analyzed in semi-empirical calculations, revealing energetic preferences for planar or slightly twisted s-cis and 'U-shaped' geometries.

  DOI：

  10.1002/1522-2675(200207)85:7<2169::aid-hlca2169>3.0.co;2-z
• 作为产物：
  描述：

  3-cyclohexylidene-1-triisopropylsilyl-5-trimethylsilylpenta-1,4-diyne 在 Hay catalyst 四丁基氟化铵 、 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 38.0h， 生成 Triisopropyl-(3,8,13,18-tetracyclohexylidene-icosa-1,4,6,9,11,14,16,19-octaynyl)-silane
  参考文献：
  名称：

  Synthesis and Characterization of Multinanometer-Sized Expanded Dendralenes with an iso-Poly(triacetylene) Backbone

  摘要：

  A series of [n]dendralenes (n = 3, 4, 8, 3b -d (Fig. 1)) expanded with buta-1,3-diynediyl moieties between the C=C bonds were prepared by repetitive acetylenic scaffolding of 3-(cyclohexylidene)penta-1,4-diyne building blocks (Scheme). These remarkably unstable iso-poly(triacetylene) (iso-PTA) oligomers were characterized by H-1- and C-13-NMR (Fig. 3 and Table 1), IR, and UV/VIS (Figs. 4 and 6 and Table 2) spectroscopy, as well as mass spectrometry (Fig. 2). The expanded [8]dendralene contains 40 C(sp)- and C(sp(2))-atoms in the backbone and represents the longest iso-PTA oligomer prepared to date. HOMO-LUMO Gap energies were determined as a function of oligomeric length (Fig. 5 and Table 3), providing insight into the degree of T-electron delocalization in these cross-conjugated chromophores. A continous drop in the HOMO-LUMO gap with increasing number of monomeric repeating units provides evidence that cross-conjugation along the oligomeric backbone is effective to some extent. The limiting HOMO-LUMO gap energy for an infinitely long, buta-1,3-diynediyl-expanded dendralene was extrapolated to about 3.3 - 3.5 eV. The conformational preferences of the expanded dendralenes were analyzed in semi-empirical calculations, revealing energetic preferences for planar or slightly twisted s-cis and 'U-shaped' geometries.

  DOI：

  10.1002/1522-2675(200207)85:7<2169::aid-hlca2169>3.0.co;2-z