1,1-Bis(triflyloxy)ethylbenzene

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: 1,1-Bis(triflyloxy)ethylbenzene
• 英文别名: [1-Phenyl-1-(trifluoromethylsulfonyloxy)ethyl] trifluoromethanesulfonate
• 化学式: C₁₀H₈F₆O₆S₂
• 分子量: 402.292
• InChiKey: JFJUPMSRMYFCHF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  104
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为产物：
  描述：

  三氟甲磺酸 、 苯乙炔 在 HW(CO)3(C5H5) 作用下， 以 二氯甲烷-D2 为溶剂， 反应 0.08h， 以25%的产率得到1-phenyl vinyl triflate
  参考文献：
  名称：

  Ionic Hydrogenation of Alkynes by HOTf and Cp(CO)3WH

  摘要：

  Alkynes can be hydrogenated at room temperature by an ionic hydrogenation method using triflic acid (CF3SO3H) as the proton donor and a transition metal hydride (Cp(CO)(3)WH) as the hydride donor. Reaction of PhC=CH with HOTf and Cp(CO)(3)WH gives ethylbenzene as the final product in high yield. Intermediates observed in this reaction are the vinyl triflate CH2=C(Ph)(OTf) and the geminal ditriflate Ph(CH3)C(OTf)(2), which result from the addition of 1 or 2 equiv of HOTf to the C=C triple bond of the alkyne. Hydrogenation of PhC=CMe by HOTf and Cp(CO)(3)WH similarly produces propylbenzene as the ultimate product. Along with vinyl triflates, additional intermediates observed in this reaction were the cis and trans isomers of the beta-methylstyrene complex [Cp(CO)(3)W-(eta(2)-PhHC=CHCH3)](+)[OTf](-). Hydrogenation of n-butylacetylene to n-hexane does occur upon reaction with HOTf/Cp(CO)(3)WH, but is very slow. In the absence of metal hydrides, 2-methyl-1-buten-3-yne reacts with HOTf to give the vinyl triflate CH2=CMeC(OTf)=CH2, but reaction with HOTf and Cp(CO)(3)WH gives Me(2)C=C(OTf)Me. The key characteristics required for the metal hydride used in these hydrogenations are the ability to donate hydride in the presence of strong acid, and the absence of rapid decomposition of the hydride through reaction with the strong acid. Cp(CO)(3)WH meets these requirements, but HSiEt(3), while an effective hydride donor, is decomposed by HOTf on the time scale of these alkyne hydrogenation reactions.

  DOI：

  10.1021/jo00127a023

文献信息

• Ionic Hydrogenation of Alkynes by HOTf and Cp(CO)3WH
  作者：Li Luan、Jeong-Sup Song、R. Morris Bullock

  DOI：10.1021/jo00127a023

  日期：1995.11

  Alkynes can be hydrogenated at room temperature by an ionic hydrogenation method using triflic acid (CF3SO3H) as the proton donor and a transition metal hydride (Cp(CO)(3)WH) as the hydride donor. Reaction of PhC=CH with HOTf and Cp(CO)(3)WH gives ethylbenzene as the final product in high yield. Intermediates observed in this reaction are the vinyl triflate CH2=C(Ph)(OTf) and the geminal ditriflate Ph(CH3)C(OTf)(2), which result from the addition of 1 or 2 equiv of HOTf to the C=C triple bond of the alkyne. Hydrogenation of PhC=CMe by HOTf and Cp(CO)(3)WH similarly produces propylbenzene as the ultimate product. Along with vinyl triflates, additional intermediates observed in this reaction were the cis and trans isomers of the beta-methylstyrene complex [Cp(CO)(3)W-(eta(2)-PhHC=CHCH3)](+)[OTf](-). Hydrogenation of n-butylacetylene to n-hexane does occur upon reaction with HOTf/Cp(CO)(3)WH, but is very slow. In the absence of metal hydrides, 2-methyl-1-buten-3-yne reacts with HOTf to give the vinyl triflate CH2=CMeC(OTf)=CH2, but reaction with HOTf and Cp(CO)(3)WH gives Me(2)C=C(OTf)Me. The key characteristics required for the metal hydride used in these hydrogenations are the ability to donate hydride in the presence of strong acid, and the absence of rapid decomposition of the hydride through reaction with the strong acid. Cp(CO)(3)WH meets these requirements, but HSiEt(3), while an effective hydride donor, is decomposed by HOTf on the time scale of these alkyne hydrogenation reactions.