4-isopropylidenecyclohexanol-1-d

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-isopropylidenecyclohexanol-1-d
• 英文别名: 1-Deuterio-4-propan-2-ylidenecyclohexan-1-ol
• 化学式: C₉H₁₆O
• 分子量: 141.218
• InChiKey: BHGNYQMQMOKBDW-QOWOAITPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  甲基磺酰氯 、 4-isopropylidenecyclohexanol-1-d 在 吡啶 作用下， 以87%的产率得到4-isopropylidenecyclohexyl-1-d mesylate
  参考文献：
  名称：

  The Interaction of π Orbitals with a Carbocation over Three σ Bonds

  摘要：

  The semi-pi analogue of double hyperconjugation (''hyperconjugation/conjugation'') has been examined in 4-isopropylidenecyclohexyl mesylate (4-OMs) by comparison with the saturated analogue, trans-4-isopropylcyclohexyl mesylate(5-OMs). The unsaturated substrate reacts in 97% trifluoroethanol only four times faster than the saturated substrate. Raber-Harris plots indicate that both substrates react by k(s) mechanisms; i.e., solvolysis occurs with solvent assistance rather than carbocation formation. These results are consistent with the absence of a direct, through-bond interaction of the double bond with the reactive center. The absence is caused at least in part by less than ideal overlap of the gamma, delta pi orbitals with the alpha,beta sigma orbitals. In contrast, an electron-rich tin atom attached to the 4-position provides a large rate enhancement and changes the mechanism to carbocation formation through double hyperconjugation.

  DOI：

  10.1021/jo951643d
• 作为产物：
  描述：

  4-isopropylidenecyclohexanone 在 硼氘化钠 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以61%的产率得到4-isopropylidenecyclohexanol-1-d
  参考文献：
  名称：

  The Interaction of π Orbitals with a Carbocation over Three σ Bonds

  摘要：

  The semi-pi analogue of double hyperconjugation (''hyperconjugation/conjugation'') has been examined in 4-isopropylidenecyclohexyl mesylate (4-OMs) by comparison with the saturated analogue, trans-4-isopropylcyclohexyl mesylate(5-OMs). The unsaturated substrate reacts in 97% trifluoroethanol only four times faster than the saturated substrate. Raber-Harris plots indicate that both substrates react by k(s) mechanisms; i.e., solvolysis occurs with solvent assistance rather than carbocation formation. These results are consistent with the absence of a direct, through-bond interaction of the double bond with the reactive center. The absence is caused at least in part by less than ideal overlap of the gamma, delta pi orbitals with the alpha,beta sigma orbitals. In contrast, an electron-rich tin atom attached to the 4-position provides a large rate enhancement and changes the mechanism to carbocation formation through double hyperconjugation.

  DOI：

  10.1021/jo951643d

文献信息

• The Interaction of π Orbitals with a Carbocation over Three σ Bonds
  作者：Joseph B. Lambert、Sol M. Ciro

  DOI：10.1021/jo951643d

  日期：1996.1.1

  The semi-pi analogue of double hyperconjugation (''hyperconjugation/conjugation'') has been examined in 4-isopropylidenecyclohexyl mesylate (4-OMs) by comparison with the saturated analogue, trans-4-isopropylcyclohexyl mesylate(5-OMs). The unsaturated substrate reacts in 97% trifluoroethanol only four times faster than the saturated substrate. Raber-Harris plots indicate that both substrates react by k(s) mechanisms; i.e., solvolysis occurs with solvent assistance rather than carbocation formation. These results are consistent with the absence of a direct, through-bond interaction of the double bond with the reactive center. The absence is caused at least in part by less than ideal overlap of the gamma, delta pi orbitals with the alpha,beta sigma orbitals. In contrast, an electron-rich tin atom attached to the 4-position provides a large rate enhancement and changes the mechanism to carbocation formation through double hyperconjugation.