methyl(phenyl)silylene | 54731-53-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl(phenyl)silylene
• 英文别名: Methylphenylsilane
• CAS: 54731-53-2
• 化学式: C₇H₈Si
• 分子量: 120.226
• InChiKey: LAQFLZHBVPULPL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.06
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 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：

  methyl(phenyl)silylene 在 氧气 作用下， 生成 methyl(phenoxy)silanone 、 methyl(phenyl)dioxasilirane
  参考文献：
  名称：

  Oxidation of Methyl(phenyl)silyleneSynthesis of a Dioxasilirane

  摘要：

  The oxidation of methyl(phenyl)silylene, 3f, with molecular oxygen is investigated using matrix isolation spectroscopy in combination with DFT calculations. The UV irradiation (lambda > 305 nm) of phenylsilyldiazomethane, 8, matrix-isolated in argon at 10 K, produces silylene 3f in very high yield. In O-2 doped argon matrixes, the thermal reaction of 3f with O-2 could be directly monitored by IR spectroscopy. The only reaction product is dioxasilirane 5f, presumably formed via cyclization of silanone O-oxide 4f. DFT calculations reveal that the activation barrier for the 4f --> 5f cyclization is less than 1 kcal/mol, too small to allow the matrix isolation of 4f. Dioxasilirane 5f is photolabile, and irradiation with blue light (lambda > 420 nm) results in a [1,2]-phenyl migration to give silaester 7f. The product of the methyl migration, silaester 13, is formed as a minor constituent.

  DOI：

  10.1021/ja000192y
• 作为产物：
  描述：

  phenylsilyl trifluoromethanesulfonate 在 N,N-二异丙基乙胺 作用下， 以 乙醚 为溶剂， 生成 methyl(phenyl)silylene
  参考文献：
  名称：

  Oxidation of Methyl(phenyl)silyleneSynthesis of a Dioxasilirane

  摘要：

  The oxidation of methyl(phenyl)silylene, 3f, with molecular oxygen is investigated using matrix isolation spectroscopy in combination with DFT calculations. The UV irradiation (lambda > 305 nm) of phenylsilyldiazomethane, 8, matrix-isolated in argon at 10 K, produces silylene 3f in very high yield. In O-2 doped argon matrixes, the thermal reaction of 3f with O-2 could be directly monitored by IR spectroscopy. The only reaction product is dioxasilirane 5f, presumably formed via cyclization of silanone O-oxide 4f. DFT calculations reveal that the activation barrier for the 4f --> 5f cyclization is less than 1 kcal/mol, too small to allow the matrix isolation of 4f. Dioxasilirane 5f is photolabile, and irradiation with blue light (lambda > 420 nm) results in a [1,2]-phenyl migration to give silaester 7f. The product of the methyl migration, silaester 13, is formed as a minor constituent.

  DOI：

  10.1021/ja000192y
• 作为试剂：
  描述：

  3-phenyl-1,6-heptadiene 在 四氟硼酸-二乙醚络合物 、 potassium fluoride 、 <(Cp^TMS)2YMe>2 、 methyl(phenyl)silylene 、 双氧水 、 potassium hydrogencarbonate 作用下， 生成 (+/-)-2-phenylcyclohexanemethanol 、 (4-苯基环己基)甲醇
  参考文献：
  名称：

  Catalytic Cyclization/Silylation of Dienes Containing 1,1-Disubstituted Olefins Using Organolanthanide and Group 3 Organometallic Complexes

  摘要：

  The catalytic cyclization/silylation reaction of hindered dienes has been investigated using the relatively unhindered complexes Me2Si(C5H3SiMe3)(2)YCH(TMS)(2) and [Cp(2)(TMS)LnMe](2) (Ln = Y, Lu). A nide variety of dienes and trienes bearing a number of functional groups were cyclized, affording silanes containing quaternary centers in a diastereoselective fashion and in good yield. The products can be oxidized using one of several different protocols, yielding alcohols for further functionalization.

  DOI：

  10.1021/jo972359k