(cyclopropylmethyl)dimethyl(2,2,2-trifluoroethoxy)silane | 141118-87-8

• 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: (cyclopropylmethyl)dimethyl(2,2,2-trifluoroethoxy)silane
• 英文别名: Cyclopropylmethyl-dimethyl-(2,2,2-trifluoroethoxy)silane
• CAS: 141118-87-8
• 化学式: C₈H₁₅F₃OSi
• 分子量: 212.287
• InChiKey: UEDWBRWYFNVDHF-UHFFFAOYSA-N

物化性质

• 沸点：
  149.3±35.0 °C(Predicted)
• 密度：
  1.067±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.18
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  二碘甲烷 、 dimethyl(2-propenyl)(2,2,2-trifluoroethoxy)silane 在 copper(l) chloride 、 锌 作用下， 以 乙醚 为溶剂， 反应 45.0h， 以49.7%的产率得到(cyclopropylmethyl)dimethyl(2,2,2-trifluoroethoxy)silane
  参考文献：
  名称：

  The far-UV photochemistry of five- and six-membered-ring monosilacycloalkenes in alcohols: stereospecific .beta.-cleavage to silyl ethers and stereoselective formation of silacycloalkyl ethers

  摘要：

  Photoalcoholysis of 1,1-dimethylsilacyclopent-2-ene (9) at 214 nm in methanol, 2,2,2-trifluoroethanol, and tert-butyl alcohol affords alkoxy(3-butenyl)dimethylsilanes 11 and 3-alkoxy-1,1-dimethylsilacyclopentanes 12. Also formed are alkoxy(cyclopropylmethyl)silanes 13 from apparent 1,3-C migration. In pure, deuterated alcohols (CH3OD and CF3CD2OD) adducts It and 12 become trans deuterated, whereas in dilute solutions of methanol-O-d in pentane, scrambling of deuterium between the trans and cis C-2 positions of 12 is observed without corresponding loss of stereospecificity for formation of silyl ether 11. Silyl ether 11 is thus produced via a pathway which is mechanistically distinct from that giving 12, for which the loss of stereoselectivity in dilute alcohols is ascribed to pseudorotational scrambling of deuterium in a silacyclopentyl cation intermediate. At high concentrations of alcohol the trans-stereoselective deuteration of 12 can be attributed to least hindered anti attack of the alcohol at C-3 of this hyperconjugatively stabilized cation. High cis-stereoselective deuteration of 12 is observed for photolysis in dilute CF3CD2OD in pentane, possibly reflecting the intermediacy of an ion pair or unsymmetrically solvated silacyclopentyl cation. Photoalcoholyses of the silacyclohex-2-ene were conducted for comparison.

  DOI：

  10.1021/jo00037a030

文献信息

• The far-UV photochemistry of five- and six-membered-ring monosilacycloalkenes in alcohols: stereospecific .beta.-cleavage to silyl ethers and stereoselective formation of silacycloalkyl ethers
  作者：Mark G. Steinmetz、Changjun Yu

  DOI：10.1021/jo00037a030

  日期：1992.5

  Photoalcoholysis of 1,1-dimethylsilacyclopent-2-ene (9) at 214 nm in methanol, 2,2,2-trifluoroethanol, and tert-butyl alcohol affords alkoxy(3-butenyl)dimethylsilanes 11 and 3-alkoxy-1,1-dimethylsilacyclopentanes 12. Also formed are alkoxy(cyclopropylmethyl)silanes 13 from apparent 1,3-C migration. In pure, deuterated alcohols (CH3OD and CF3CD2OD) adducts It and 12 become trans deuterated, whereas in dilute solutions of methanol-O-d in pentane, scrambling of deuterium between the trans and cis C-2 positions of 12 is observed without corresponding loss of stereospecificity for formation of silyl ether 11. Silyl ether 11 is thus produced via a pathway which is mechanistically distinct from that giving 12, for which the loss of stereoselectivity in dilute alcohols is ascribed to pseudorotational scrambling of deuterium in a silacyclopentyl cation intermediate. At high concentrations of alcohol the trans-stereoselective deuteration of 12 can be attributed to least hindered anti attack of the alcohol at C-3 of this hyperconjugatively stabilized cation. High cis-stereoselective deuteration of 12 is observed for photolysis in dilute CF3CD2OD in pentane, possibly reflecting the intermediacy of an ion pair or unsymmetrically solvated silacyclopentyl cation. Photoalcoholyses of the silacyclohex-2-ene were conducted for comparison.