5,5'-dibromo-1,1,1',1'-tetraethyl-3,3',4,4'-tetraphenyl-2,2'-bisilole | 160319-33-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 5,5'-dibromo-1,1,1',1'-tetraethyl-3,3',4,4'-tetraphenyl-2,2'-bisilole
• 英文别名: 5,5'-dibromo-1,1,1',1'-tetraethyl-3,3',4,4'-tetraphenyl-2,2'-bisilol；2-Bromo-5-(5-bromo-1,1-diethyl-3,4-diphenylsilol-2-yl)-1,1-diethyl-3,4-diphenylsilole
• CAS: 160319-33-5
• 化学式: C₄₀H₄₀Br₂Si₂
• 分子量: 736.737
• InChiKey: RGQUGDJJLBQADD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.67
• 重原子数：
  44
• 可旋转键数：
  9
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  5,5'-dibromo-1,1,1',1'-tetraethyl-3,3',4,4'-tetraphenyl-2,2'-bisilole 在 对二硝基苯 、 四甲基乙二胺 、 叔丁基锂 作用下， 生成 5,5'''-dibromo-1,1,1',1',1'',1'',1''',1'''-octaethyl-3,3',3'',3''',4,4',4'',4'''-octaphenyl-2,2':5',2'':5'',2'''-quatersilole
  参考文献：
  名称：

  Oligosiloles: First Synthesis Based on a Novel Endo-Endo Mode Intramolecular Reductive Cyclization of Diethynylsilanes

  摘要：

  A general and versatile synthesis of 2,5-difunctional siloles and their conversion into oligosiloles are described. Diethynylsilanes undergo intramolecular reductive cyclization in an endo-endo mode upon treatment with lithium naphthalenide to form 2,5-dilithiosiloles. The 2,5-dilithiosiloles ate converted into various 2,5-difunctional siloles by treatment with electrophiles. The resulting 2,5-dibromosilole is further converted into several highly functionalized siloles via palladium-catalyzed cross-coupling reaction or selective mono-lithiation using n-butyllithium in ether. Oligosiloles, from bisiloles to quatersilole, are prepared from certain functional siloles. Oxidative coupling of 2,5-dilithiosilole by use of an Fe(III) complex affords 2,2'-bisilole as yellow crystals. Difunctional oligosiloles, 5,5'-dibromo-2,2'-bisilole and 5,5'''-dibromo-2,2':5',2'':5'',2'''-quatersilole, are prepared by oxidative coupling via higher order cyanocuprate of 2-bromo-5-lithiosilole and 5-bromo-5'-lithio-2,2'-bisilole, respectively. X-ray crystal structures of these bisiloles show highly twisted arrangements between two silole rings with 62-64 degrees of torsion angle. H-1 NMR studies on bisiloles show a rapid equilibration between non-coplanar conformers in solution. In UV-visible spectra, nevertheless, all of the oligosiloles have unusually long absorption maxima.

  DOI：

  10.1021/ja00105a012
• 作为产物：
  描述：

  2,5-dibromo-1,1-diethyl-3,4-diphenylsilole 在 对二硝基苯 、 正丁基锂 、 四甲基乙二胺 作用下， 生成 5,5'-dibromo-1,1,1',1'-tetraethyl-3,3',4,4'-tetraphenyl-2,2'-bisilole
  参考文献：
  名称：

  Oligosiloles: First Synthesis Based on a Novel Endo-Endo Mode Intramolecular Reductive Cyclization of Diethynylsilanes

  摘要：

  A general and versatile synthesis of 2,5-difunctional siloles and their conversion into oligosiloles are described. Diethynylsilanes undergo intramolecular reductive cyclization in an endo-endo mode upon treatment with lithium naphthalenide to form 2,5-dilithiosiloles. The 2,5-dilithiosiloles ate converted into various 2,5-difunctional siloles by treatment with electrophiles. The resulting 2,5-dibromosilole is further converted into several highly functionalized siloles via palladium-catalyzed cross-coupling reaction or selective mono-lithiation using n-butyllithium in ether. Oligosiloles, from bisiloles to quatersilole, are prepared from certain functional siloles. Oxidative coupling of 2,5-dilithiosilole by use of an Fe(III) complex affords 2,2'-bisilole as yellow crystals. Difunctional oligosiloles, 5,5'-dibromo-2,2'-bisilole and 5,5'''-dibromo-2,2':5',2'':5'',2'''-quatersilole, are prepared by oxidative coupling via higher order cyanocuprate of 2-bromo-5-lithiosilole and 5-bromo-5'-lithio-2,2'-bisilole, respectively. X-ray crystal structures of these bisiloles show highly twisted arrangements between two silole rings with 62-64 degrees of torsion angle. H-1 NMR studies on bisiloles show a rapid equilibration between non-coplanar conformers in solution. In UV-visible spectra, nevertheless, all of the oligosiloles have unusually long absorption maxima.

  DOI：

  10.1021/ja00105a012

文献信息

• Tamao Kohei, Yamaguchi Shigehiro, Shiro Motoo, J. Amer. Chem. Soc, 116 (1994) N 26, S 11715-11722
  作者：Tamao Kohei, Yamaguchi Shigehiro, Shiro Motoo

  DOI：——

  日期：——
• Oligosiloles: First Synthesis Based on a Novel Endo-Endo Mode Intramolecular Reductive Cyclization of Diethynylsilanes
  作者：Kohei Tamao、Shigehiro Yamaguchi、Motoo Shiro

  DOI：10.1021/ja00105a012

  日期：1994.12

  A general and versatile synthesis of 2,5-difunctional siloles and their conversion into oligosiloles are described. Diethynylsilanes undergo intramolecular reductive cyclization in an endo-endo mode upon treatment with lithium naphthalenide to form 2,5-dilithiosiloles. The 2,5-dilithiosiloles ate converted into various 2,5-difunctional siloles by treatment with electrophiles. The resulting 2,5-dibromosilole is further converted into several highly functionalized siloles via palladium-catalyzed cross-coupling reaction or selective mono-lithiation using n-butyllithium in ether. Oligosiloles, from bisiloles to quatersilole, are prepared from certain functional siloles. Oxidative coupling of 2,5-dilithiosilole by use of an Fe(III) complex affords 2,2'-bisilole as yellow crystals. Difunctional oligosiloles, 5,5'-dibromo-2,2'-bisilole and 5,5'''-dibromo-2,2':5',2'':5'',2'''-quatersilole, are prepared by oxidative coupling via higher order cyanocuprate of 2-bromo-5-lithiosilole and 5-bromo-5'-lithio-2,2'-bisilole, respectively. X-ray crystal structures of these bisiloles show highly twisted arrangements between two silole rings with 62-64 degrees of torsion angle. H-1 NMR studies on bisiloles show a rapid equilibration between non-coplanar conformers in solution. In UV-visible spectra, nevertheless, all of the oligosiloles have unusually long absorption maxima.