1-Ethoxy-3-tert-butylallene | 928-62-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-Ethoxy-3-tert-butylallene
• 英文别名: 1-Ethoxy-4,4-dimethyl-pentadien-(1,2)；1-ethoxy-4,4-dimethyl-penta-1,2-diene
• CAS: 928-62-1
• 化学式: C₉H₁₆O
• 分子量: 140.225
• InChiKey: SMTRAOREUGLJMJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-Ethoxy-3-tert-butylallene 在 [(6)Li]-n-butyllithium 作用下， 以 正己烷 为溶剂， 反应 0.17h， 生成 1-(6)Lithio-1-ethoxy-3-tert-butylallene
  参考文献：
  名称：

  Experimental and theoretical investigations on the structure and reactivity of .alpha.-lithiomethoxyallene and its Grignard analog

  摘要：

  C-13 NMR, Li-6,H-1-HOESY-NMR, and IR spectroscopy of alpha-lithiomethoxyallene (7) and 1-lithio-1-ethoxy-3-tert-butylallene (8) as well as ab initio model calculations on monomeric and dimeric alpha-lithiohydroxyallene prove 7 and 8 to be dimeric in THF (7 forms a tetramer in diethyl ether) with a nonclassically 1,3-bridged structure. Alternative oxygen-coordinated structures could be excluded definitely. Ab initio calculations indicate that the methoxyallene a-Grignard derivative either has a classic allenic structure or an O-coordinated allenic form (or is a mixture of both) in solution. An alternative propargylic-type isomer is unfavorable energetically. Model computed reactions with hydrogen as the electrophile indicate that the regiospecific alpha-substitution of alpha-lithiomethoxyallene is favored kinetically over the-gamma-substitution. In contrast, the reaction of the classic (alpha-hydroxyallenyl)-magnesium hydride with an electrophile leads to the formation of an alkyne (by gamma-substitution) while that of the O-coordinated isomer yields the corresponding allene (by alpha-substitution).

  DOI：

  10.1021/jo00075a036

文献信息

• Reactivity of allyl-zinc (and copper) reagents towards allenic ethers and α-metallated allenic ethers
  作者：J.-F. Normant、J.-Ch. Quirion、Y. Masuda、A. Alexakis

  DOI：10.1016/0040-4039(90)80172-i

  日期：1990.1
• NORMANT, J. -F.;QUIRION, J. -CH.;MASUDA, Y.;ALEXAKIS, A., TETRAHEDRON LETT., 31,(1990) N0, C. 2879-2882
  作者：NORMANT, J. -F.、QUIRION, J. -CH.、MASUDA, Y.、ALEXAKIS, A.

  DOI：——

  日期：——
• Experimental and theoretical investigations on the structure and reactivity of .alpha.-lithiomethoxyallene and its Grignard analog
  作者：Christoph Lambert、Paul v. R. Schleyer、Ernst Ulrich Wuerthwein

  DOI：10.1021/jo00075a036

  日期：1993.11

  C-13 NMR, Li-6,H-1-HOESY-NMR, and IR spectroscopy of alpha-lithiomethoxyallene (7) and 1-lithio-1-ethoxy-3-tert-butylallene (8) as well as ab initio model calculations on monomeric and dimeric alpha-lithiohydroxyallene prove 7 and 8 to be dimeric in THF (7 forms a tetramer in diethyl ether) with a nonclassically 1,3-bridged structure. Alternative oxygen-coordinated structures could be excluded definitely. Ab initio calculations indicate that the methoxyallene a-Grignard derivative either has a classic allenic structure or an O-coordinated allenic form (or is a mixture of both) in solution. An alternative propargylic-type isomer is unfavorable energetically. Model computed reactions with hydrogen as the electrophile indicate that the regiospecific alpha-substitution of alpha-lithiomethoxyallene is favored kinetically over the-gamma-substitution. In contrast, the reaction of the classic (alpha-hydroxyallenyl)-magnesium hydride with an electrophile leads to the formation of an alkyne (by gamma-substitution) while that of the O-coordinated isomer yields the corresponding allene (by alpha-substitution).