1-methyl-3,5,6-tris(trimethylsilyl)cyclohexa-1,3-diene | 142565-93-3

• 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-methyl-3,5,6-tris(trimethylsilyl)cyclohexa-1,3-diene
• 英文别名: trimethyl-[(1S,6S)-2-methyl-4,6-bis(trimethylsilyl)cyclohexa-2,4-dien-1-yl]silane
• CAS: 142565-93-3；142565-94-4
• 化学式: C₁₆H₃₄Si₃
• 分子量: 310.702
• InChiKey: RPWPJMSXCBNPDO-HOTGVXAUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.17
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  三甲基氯硅烷 、 3-氯甲苯 在 N,N,N,N-tetraethylammonium tetrafluoroborate 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 为溶剂， 以8%的产率得到三甲基-(3-甲基苯基)硅烷
  参考文献：
  名称：

  The electrochemical reductive trimethylsilylation of aryl chlorides: a good route to aryltrimethylsilanes and a novel route to tris(trimethylsilyl)cyclohexadienes

  摘要：

  The electroreductive trimethylsilylation of aryl chlorides R-C6H4Cl (R = H, o-Me, m-Me, p-Me) can be controlled so as to give, in good yields, either the corresponding aryltrimethylsilanes (products of the reduction of the carbon-chlorine bond) or mixtures of cis- and trans-tris(trimethylsilyl)cyclohexa-1,3(or 1,4)-dienes (products of the successive reduction of the carbon-chlorine bond and the partial reduction of the aromatic ring). Which of the two products is formed depends upon how much electricity is passed during the constant current electrolysis, in a one-compartment cell equipped with a sacrificial aluminum anode, of an aryl chloride in 80:20 THF/HMPA solution that also contains Et4NBF4 as the supporting electrolyte and excess Me3SiCl. The electroreductive trimethylsilylation of phenyltrimethylsilane gave, in 62% yield, a mixture of three 3,5,6-tris(trimethylsilyl)-cyclohexa-1,3-dienes, of which the trans, pseudo a-a isomer constituted 89%. Such products cannot be obtained by the chemoreductive trimethylsilylation of phenyltrimethylsilane. The electroreductive trimethylsilylation of benzene and toluene produced the corresponding bis(trimethylsilyl)cyclohexa-1,4-dienes. The regio- and stereochemical outcomes of the electroreductive trimethylsilylation of the various substrates can be explained in terms of the electronic and steric effets of the substituents originally attached to the aromatic ring and the steric effects of the trimethylsilyl groups that are subsequently attached.

  DOI：

  10.1021/jo00043a031

文献信息

• The electrochemical reductive trimethylsilylation of aryl chlorides: a good route to aryltrimethylsilanes and a novel route to tris(trimethylsilyl)cyclohexadienes
  作者：Michel Bordeau、Claude Biran、Pierrette Pons、Marie Pierre Leger-Lambert、Jacques Dunogues

  DOI：10.1021/jo00043a031

  日期：1992.8

  The electroreductive trimethylsilylation of aryl chlorides R-C6H4Cl (R = H, o-Me, m-Me, p-Me) can be controlled so as to give, in good yields, either the corresponding aryltrimethylsilanes (products of the reduction of the carbon-chlorine bond) or mixtures of cis- and trans-tris(trimethylsilyl)cyclohexa-1,3(or 1,4)-dienes (products of the successive reduction of the carbon-chlorine bond and the partial reduction of the aromatic ring). Which of the two products is formed depends upon how much electricity is passed during the constant current electrolysis, in a one-compartment cell equipped with a sacrificial aluminum anode, of an aryl chloride in 80:20 THF/HMPA solution that also contains Et4NBF4 as the supporting electrolyte and excess Me3SiCl. The electroreductive trimethylsilylation of phenyltrimethylsilane gave, in 62% yield, a mixture of three 3,5,6-tris(trimethylsilyl)-cyclohexa-1,3-dienes, of which the trans, pseudo a-a isomer constituted 89%. Such products cannot be obtained by the chemoreductive trimethylsilylation of phenyltrimethylsilane. The electroreductive trimethylsilylation of benzene and toluene produced the corresponding bis(trimethylsilyl)cyclohexa-1,4-dienes. The regio- and stereochemical outcomes of the electroreductive trimethylsilylation of the various substrates can be explained in terms of the electronic and steric effets of the substituents originally attached to the aromatic ring and the steric effects of the trimethylsilyl groups that are subsequently attached.