3-(dimethylphenylsilyl)cyclobut-1-ne | 847158-86-5

• 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: 3-(dimethylphenylsilyl)cyclobut-1-ne
• 英文别名: 3-(dimethylphenylsilyl)cyclobutene；3-(phenyldimethylsilyl)cyclobutene；(2-Cyclobuten-1-yldimethylsilyl)benzene；cyclobut-2-en-1-yl-dimethyl-phenylsilane
• CAS: 847158-86-5
• 化学式: C₁₂H₁₆Si
• 分子量: 188.345
• InChiKey: ZXYIXPUTEKMRFP-UHFFFAOYSA-N

物化性质

• 溶解度：
  可溶于二氯甲烷、乙酸乙酯、己烷

计算性质

• 辛醇/水分配系数(LogP)：
  2.93
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  苯基氯化硒 、 3-(dimethylphenylsilyl)cyclobut-1-ne 以 二氯甲烷 为溶剂， 反应 3.0h， 生成
  参考文献：
  名称：

  Contrasteric Stereochemical Dictation of the Cyclobutene Ring-Opening Reaction by a Vacant Boron p Orbital

  摘要：

  Cyclobutene, having a pinacolatoboryl group at the 3-position, was prepared by the reaction of trimethyl borate with a cyclobutenyl anion, which was generated by reductive lithiation of 3-(phenylselenyl)cyclobutene. Its thermal ring-opening reaction provided (Z)-1-borylbuta-1,3-diene selectively despite the arising steric congestion. The contrasteric behavior was accounted for by assuming an electron-accepting interaction of the vacant boron p orbital with the distorted breaking sigma orbital in the inward transition state.

  DOI：

  10.1021/ja043979n
• 作为产物：
  描述：

  3-(dimethylphenylsilyl)cyclobutanone 在 正丁基锂 、 四甲基乙二胺 作用下， 以 乙醇 、 正己烷 为溶剂， 反应 15.0h， 生成 3-(dimethylphenylsilyl)cyclobut-1-ne
  参考文献：
  名称：

  Contrasteric Stereochemical Dictation of the Cyclobutene Ring-Opening Reaction by a Vacant Boron p Orbital

  摘要：

  Cyclobutene, having a pinacolatoboryl group at the 3-position, was prepared by the reaction of trimethyl borate with a cyclobutenyl anion, which was generated by reductive lithiation of 3-(phenylselenyl)cyclobutene. Its thermal ring-opening reaction provided (Z)-1-borylbuta-1,3-diene selectively despite the arising steric congestion. The contrasteric behavior was accounted for by assuming an electron-accepting interaction of the vacant boron p orbital with the distorted breaking sigma orbital in the inward transition state.

  DOI：

  10.1021/ja043979n

文献信息

• Substituent effect of group 14 elements on the ring-opening reaction of cyclobutene
  作者：Munehiro Hasegawa、Ippei Usui、Soichiro Konno、Masahiro Murakami

  DOI：10.1039/c004972g

  日期：——

  group 14 elements at the 3-position were synthesized, and their thermal ring-opening reactions were studied. Carbon-substituted cyclobutene underwent the ring-opening reaction through an outward pathway to afford the E-diene exclusively. On the other hand, the ring-opening reaction of the silyl, germyl, and stannyl substituted cyclobutenes occurred in both outward and inward directions giving a mixture

  合成了一系列在3位带有14族元素的环丁烯，并研究了它们的热开环反应。 碳取代的 环丁烯通过向外的途径进行开环反应，仅得到E-二烯。另一方面，甲硅烷基，癸基和苯乙​​烯基取代的环丁烯的开环反应在向外和向内均发生，得到E和Z异构体的混合物。计算的过渡态和总体分析的结构特征表明，Z异构体的形成可归因于HOMO与第14组元素的σ *轨道之间的供体/受体相互作用。有趣的是，内向偏好的顺序是硅 > 锡 > 通用电器。通过考虑能隙和σ *轨道与HOMO之间的重叠量，来解释甲硅烷基，癸基和苯乙​​烯基取代基的这些旋转行为。