1-(bromoethynyl)-4-((trimethylsilyl)ethynyl)cubane | 163333-00-4

• 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: 1-(bromoethynyl)-4-((trimethylsilyl)ethynyl)cubane
• 英文别名: 2-[4-(2-bromoethynyl)cuban-1-yl]ethynyl-trimethylsilane
• CAS: 163333-00-4
• 化学式: C₁₅H₁₅BrSi
• 分子量: 303.274
• InChiKey: GCCVRZWMCCSTNU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.96
• 重原子数：
  17.0
• 可旋转键数：
  0.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.73
• 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：

  1-乙炔基立方烷 、 1-(bromoethynyl)-4-((trimethylsilyl)ethynyl)cubane 在 吡啶 、 正丁基锂 、 copper(I) bromide 作用下， 生成 1-(4-((trimethylsilyl)ethynyl)cubyl)-4-cubyl-1,3-butadiyne
  参考文献：
  名称：

  Alkynylcubanes as Precursors of Rigid-Rod Molecules and Alkynylcyclooctatetraenes

  摘要：

  We have developed new methodology for the synthesis of alkynylcubanes and have used these compounds to make rigid-rod molecules constructed of cubane and acetylene subunits. Terminal and substituted alkynylcubanes 7a, 7b, 8a, 8b, 12a, and 12b were synthesized by n-BuLi-promoted elimination of halogen from 1,1-dibromovinylcubanes 6a, 6b, and 11, followed by quenching with electrophiles. Systems with one or two acetylenic units between two cubanes were also prepared: dicubylacetylene (15) was obtained via reaction of the lithium ylide of (trimethylsilyl)diazomethane with dicubyl ketone (14); 1,4-dicubyl-1,3-butadiyne (16) was made by oxidative dimerization of ethynylcubane (7a). Dimerizations and cross-coupling reactions of various 1,4-diethynylcubanes afforded longer rods, e.g., 1,4-bis-((trimethylsilyl)ethynyl)cubyl- 1,3-butadiyne (18) and 1-(4-((trimethylsilyl)ethynyl)cubyl)-4-cubyl-1,3-butadiyne (21). Rh(I)-promoted ring opening of the cubane subunit(s) of these compounds into the corresponding tricyclooctadiene followed by thermal rearrangement to the cyclooctatetraene was used to convert 7a, 8a, and 12a into the mono- and disubstituted alkynylcyclooctatetraenes 22a, 22b, and 23 and to take 15 and 16 into the alkynyl-bridged cyclooctatetraenes 24a and 24b, respectively. X-ray crystallographic analysis of 12a, 15, 16, and 18 revealed interesting details about their structures.

  DOI：

  10.1021/ja00096a016
• 作为产物：
  描述：

  1,4-diethynylcubane 在 N-溴代丁二酰亚胺(NBS) 、 正丁基锂 、 methyllithium lithium bromide 作用下， 反应 17.83h， 生成 1-(bromoethynyl)-4-((trimethylsilyl)ethynyl)cubane
  参考文献：
  名称：

  Alkynylcubanes as Precursors of Rigid-Rod Molecules and Alkynylcyclooctatetraenes

  摘要：

  We have developed new methodology for the synthesis of alkynylcubanes and have used these compounds to make rigid-rod molecules constructed of cubane and acetylene subunits. Terminal and substituted alkynylcubanes 7a, 7b, 8a, 8b, 12a, and 12b were synthesized by n-BuLi-promoted elimination of halogen from 1,1-dibromovinylcubanes 6a, 6b, and 11, followed by quenching with electrophiles. Systems with one or two acetylenic units between two cubanes were also prepared: dicubylacetylene (15) was obtained via reaction of the lithium ylide of (trimethylsilyl)diazomethane with dicubyl ketone (14); 1,4-dicubyl-1,3-butadiyne (16) was made by oxidative dimerization of ethynylcubane (7a). Dimerizations and cross-coupling reactions of various 1,4-diethynylcubanes afforded longer rods, e.g., 1,4-bis-((trimethylsilyl)ethynyl)cubyl- 1,3-butadiyne (18) and 1-(4-((trimethylsilyl)ethynyl)cubyl)-4-cubyl-1,3-butadiyne (21). Rh(I)-promoted ring opening of the cubane subunit(s) of these compounds into the corresponding tricyclooctadiene followed by thermal rearrangement to the cyclooctatetraene was used to convert 7a, 8a, and 12a into the mono- and disubstituted alkynylcyclooctatetraenes 22a, 22b, and 23 and to take 15 and 16 into the alkynyl-bridged cyclooctatetraenes 24a and 24b, respectively. X-ray crystallographic analysis of 12a, 15, 16, and 18 revealed interesting details about their structures.

  DOI：

  10.1021/ja00096a016

文献信息

• Eaton Philip E., Galoppini Elena, Gilardi Richard, J. Amer. Chem. Soc, 116 (1994) N 17, S 7588-7596
  作者：Eaton Philip E., Galoppini Elena, Gilardi Richard

  DOI：——

  日期：——