1-methyl-1-propyl-3,4-benzosilacyclobutene | 325461-94-7

• 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-1-propyl-3,4-benzosilacyclobutene
• 英文别名: 7-Methyl-7-propyl-7-silabicyclo[4.2.0]octa-1,3,5-triene；7-methyl-7-propyl-7-silabicyclo[4.2.0]octa-1,3,5-triene
• CAS: 325461-94-7
• 化学式: C₁₁H₁₆Si
• 分子量: 176.334
• InChiKey: ZXYMNWQNYFYAAV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.48
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 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：

  甲醇 、 1-methyl-1-propyl-3,4-benzosilacyclobutene 反应 14.0h， 以76%的产率得到methylmethoxy(o-tolyl)(1-propyl)silane
  参考文献：
  名称：

  The one- and two-photon photochemistry of benzylsilacyclobutanes, acyclic benzylsilanes, and 1,1,2-triphenylsilacyclobutane

  摘要：

  已完成。

  DOI：

  10.1139/v99-249
• 作为产物：
  描述：

  1-benzyl-1-methylsilacyclobutane 在 甲醇 作用下， 以 正己烷 为溶剂， 反应 59.0h， 以98%的产率得到1-methyl-1-propyl-3,4-benzosilacyclobutene
  参考文献：
  名称：

  The one- and two-photon photochemistry of benzylsilacyclobutanes, acyclic benzylsilanes, and 1,1,2-triphenylsilacyclobutane

  摘要：

  已完成。

  DOI：

  10.1139/v99-249

文献信息

• The one- and two-photon photochemistry of benzylsilacyclobutanes, acyclic benzylsilanes, and 1,1,2-triphenylsilacyclobutane
  作者：William J Leigh、Thomas R Owens

  DOI：10.1139/v99-249

  日期：2000.11.1

  The photochemistry of several α-silylbenzyl compounds has been investigated in hexane and in methanol solution. Direct photolysis of 1-benzyl-1-methylsilacyclobutane (1) in methanolic hexane solution produces 1-propyl-1-methyl-2,3-benzosilacyclobutene (6) in quantitative yield, by a sequential two-photon process involving the photoactive isotoluene derivative 1-methylene-6-(1-methylsilacyclobutyl)-2,4-cyclohexadiene (13a), which has been identified on the basis of its ¹H NMR and UV absorption spectra. In contrast, direct irradiation of 1-benzyl-1-phenylsilacyclobutane (2) under similar conditions results in the formation of a complex mixture of products consistent with the competing formation of 1-benzyl-1-phenylsilene and benzyl- and 1-phenylsilacyclobutyl radicals. The silene is a transient which has been detected directly by laser flash photolysis of 2 (λ_max = 315 nm, τ ~ 4.5 µs). Free radical formation is shown to be due to secondary photolysis of a second primary product, 1-methylene-6-(1-phenylsilacyclobutyl)-2,4-cyclohexadiene (13b), which has also been detected and identified by static UV absorption (λ_max = 335 nm) and ¹H NMR spectroscopy. In a reaction with some analogy to the acid-catalyzed desilylation of allylsilanes, both 13a and 13b can be intercepted in neutral or acidic methanol solution to yield toluene and 1-methyl- or 1-phenyl-1-methoxysilacyclobutane, respectively. Direct photolysis of benzyldimethylphenylsilane (4) also leads to the formation of the corresponding isotoluene derivative, while benzyltrimethylsilane (3) exhibits negligible photoreactivity. The endocyclic benzylsilane 1,1,2-triphenylsilacyclobutane (5) is shown to undergo competing [2 + 2]-cycloreversion and [1,3]-silyl migration to yield a bicyclic isotoluene analogue, which reacts rapidly with methanol to yield the acyclic methoxysilane reported previously to be the main product of photolysis of this silacyclobutane in methanol solution. Relative quantum yields for isotoluene formation from photolysis of 1-4 and absolute rate constants for methanolysis of several of these compounds under neutral and acidic conditions have also been determined.Key words: photochemistry, organosilicon, benzylsilane, silacyclobutane, silene, kinetics, isotoluene.

  已完成。