Triethyl-[[6,9,18-tris(triethylsilyloxy)-1-hexacyclo[16.2.2.22,5.26,9.210,13.214,17]triaconta-2(30),3,5(29),7,10(26),11,13(25),14,16,19,21,23,27-tridecaenyl]oxy]silane | 1552276-81-9

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: Triethyl-[[6,9,18-tris(triethylsilyloxy)-1-hexacyclo[16.2.2.22,5.26,9.210,13.214,17]triaconta-2(30),3,5(29),7,10(26),11,13(25),14,16,19,21,23,27-tridecaenyl]oxy]silane
• 英文别名: triethyl-[[6,9,18-tris(triethylsilyloxy)-1-hexacyclo[16.2.2.22,5.26,9.210,13.214,17]triaconta-2(30),3,5(29),7,10(26),11,13(25),14,16,19,21,23,27-tridecaenyl]oxy]silane
• CAS: 1552276-81-9
• 化学式: C₅₄H₈₀O₄Si₄
• 分子量: 905.569
• InChiKey: QCDJTEORBDRNMX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  16.19
• 重原子数：
  62
• 可旋转键数：
  20
• 环数：
  16.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Triethyl-[[6,9,18-tris(triethylsilyloxy)-1-hexacyclo[16.2.2.22,5.26,9.210,13.214,17]triaconta-2(30),3,5(29),7,10(26),11,13(25),14,16,19,21,23,27-tridecaenyl]oxy]silane 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以96%的产率得到Hexacyclo[16.2.2.22,5.26,9.210,13.214,17]triaconta-2(30),3,5(29),7,10(26),11,13(25),14,16,19,21,23,27-tridecaene-1,6,9,18-tetrol
  参考文献：
  名称：

  通过H2SnCl4介导的1,4-二羟基环-2,5-二烯前体的芳构化实际合成[n]环对亚苯基（n = 5，7-12）

  摘要：

  包含1,4-二羟基-2,5-环己二烯-1,4-二基单元的环对亚苯基（CPP）的环状前体可通过修改Jasti和同事开发的合成相应1,4-二甲氧基的合成方法来制备衍生品。SnCl 2/2 HCl在温和的条件下对二基部分进行还原性芳构化，并以5或7-12个亚苯基单元的高收率提供了CPP。高应变[5] CPP的合成规模大于0.3 g。119 Sn NMR光谱阐明了混合2：1的HCl和SnCl 2时原位形成的络合物H 2 SnCl 4的情况。，在几乎中性的条件下可作为高活性还原剂。当使用相对于SnCl 2大于2当量的HCl时，会发生CPP前体的酸催化分解。HCl和SnCl 2的化学计量对实现高度应变的CPP前体所需的芳构化反应至关重要。

  DOI：

  10.1002/chem.201406650
• 作为产物：
  描述：

  4-bromo-4'-[(tert-butyldimethylsilyl)oxy]biphenyl 在 咪唑 、 2,2'-联吡啶 、 bis(1,5-cyclooctadiene)nickel (0) 、 lithium hydroxide monohydrate 、 碘苯二乙酸 、 sodium hydride 作用下， 以 四氢呋喃 、 水 、 N,N-二甲基甲酰胺 、 乙腈 、 mineral oil 为溶剂， 反应 55.5h， 生成 Triethyl-[[6,9,18-tris(triethylsilyloxy)-1-hexacyclo[16.2.2.22,5.26,9.210,13.214,17]triaconta-2(30),3,5(29),7,10(26),11,13(25),14,16,19,21,23,27-tridecaenyl]oxy]silane
  参考文献：
  名称：

  Synthesis and Characterization of [5]Cycloparaphenylene

  摘要：

  The synthesis of highly strained [5]cycloparaphenylene ([5]CPP), a structural unit of the periphery of C-60 and the shortest possible structural constituent of the sidewall of a (5,5) carbon nanotube, was achieved in nine steps in 17% overall yield. The synthesis relied on metal-mediated ring closure of a triethylsilyl (TES)-protected masked precursor 1c followed by removal of the TES groups and subsequent reductive aromatization. UV-vis and electrochemical studies revealed that the HOMO-LUMO gap of [5]CPP is narrow and is comparable to that of C-60, as predicted by theoretical calculations. The results suggest that [5]CPP should be an excellent lead compound for molecular electronics.

  DOI：

  10.1021/ja413214q

文献信息

• Synthesis and Characterization of [5]Cycloparaphenylene
  作者：Eiichi Kayahara、Vijay Kumar Patel、Shigeru Yamago

  DOI：10.1021/ja413214q

  日期：2014.2.12

  The synthesis of highly strained [5]cycloparaphenylene ([5]CPP), a structural unit of the periphery of C-60 and the shortest possible structural constituent of the sidewall of a (5,5) carbon nanotube, was achieved in nine steps in 17% overall yield. The synthesis relied on metal-mediated ring closure of a triethylsilyl (TES)-protected masked precursor 1c followed by removal of the TES groups and subsequent reductive aromatization. UV-vis and electrochemical studies revealed that the HOMO-LUMO gap of [5]CPP is narrow and is comparable to that of C-60, as predicted by theoretical calculations. The results suggest that [5]CPP should be an excellent lead compound for molecular electronics.
• Practical Synthesis of [<i>n</i>]Cycloparaphenylenes (<i>n</i>=5, 7-12) by H₂SnCl₄-Mediated Aromatization of 1,4-Dihydroxycyclo-2,5-diene Precursors
  作者：Vijay Kumar Patel、Eiichi Kayahara、Shigeru Yamago

  DOI：10.1002/chem.201406650

  日期：2015.4.7

  synthesized in greater than 0.3 g scale. 119Sn NMR spectroscopy clarifies the in situ formation of an ate complex, H2SnCl4, upon mixing a 2:1 ratio of HCl and SnCl2, which serves as a highly active reducing agent under nearly neutral conditions. When more than 2 equivalents of HCl, in relation to SnCl2, are used, acid‐catalyzed decomposition of the CPP precursors takes place. The stoichiometry of HCl and SnCl2

  包含1,4-二羟基-2,5-环己二烯-1,4-二基单元的环对亚苯基（CPP）的环状前体可通过修改Jasti和同事开发的合成相应1,4-二甲氧基的合成方法来制备衍生品。SnCl 2/2 HCl在温和的条件下对二基部分进行还原性芳构化，并以5或7-12个亚苯基单元的高收率提供了CPP。高应变[5] CPP的合成规模大于0.3 g。119 Sn NMR光谱阐明了混合2：1的HCl和SnCl 2时原位形成的络合物H 2 SnCl 4的情况。，在几乎中性的条件下可作为高活性还原剂。当使用相对于SnCl 2大于2当量的HCl时，会发生CPP前体的酸催化分解。HCl和SnCl 2的化学计量对实现高度应变的CPP前体所需的芳构化反应至关重要。