trans-2,2,6,6-tetramethyl-3-chloro-4-heptene | 220604-76-2

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机氯化物
• 英文名称: trans-2,2,6,6-tetramethyl-3-chloro-4-heptene
• 英文别名: (3E)-5-Chloro-2,2,6,6-tetramethyl-3-heptene；(E)-5-chloro-2,2,6,6-tetramethylhept-3-ene
• CAS: 220604-76-2
• 化学式: C₁₁H₂₁Cl
• 分子量: 188.741
• InChiKey: CYCQUOVTBWNYQE-BQYQJAHWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.82
• 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：

  trans-2,2,6,6-tetramethyl-3-chloro-4-heptene 在 正丁基锂 、 N,N-二甲基-1-萘胺 、 lithium 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.0h， 生成 1,3-di-tert-butylallyllithium
  参考文献：
  名称：

  Reorientation Dynamics within Ion-Paired Allylic Lithium Compounds:  Isolation of Inversion Processes

  摘要：

  Among the several ion-ion reorientational processes that take place within several newly studied allylic Lithium compounds, the dynamics of transfer of TMEDA-coordinated lithium between the two allyl faces has been determined independently by use of C-13 NMR line shape studies of diastereotopic geminal methylsilyl groups strategically incorporated close to the chiral lithium in the organometallic species. With increasing temperature, the C-13 Shift between these methyls is progressively averaged due to faster rates of lithium transfer (inversion). Typical Delta H-double dagger values of 5-7 kcal.mol(-1) with Delta S-double dagger = ca. -20 eu are encountered. A faster process, the reorientation of coordinated TMEDA on one side of the allyl plane, has been monitored from the NCH3 C-13 resonance of TMEDA-coordinated Li+, with Delta H-double dagger = 7 kcal.mol(-1) and Delta S-double dagger = ca. -12 eu.

  DOI：

  10.1021/jo982196f
• 作为产物：
  描述：

  (E)-2,2,6,6-tetramethylhept-4-en-3-one 在 lithium aluminium tetrahydride 、 氯化亚砜 作用下， 以 乙醚 为溶剂， 反应 7.5h， 生成 trans-2,2,6,6-tetramethyl-3-chloro-4-heptene
  参考文献：
  名称：

  Reorientation Dynamics within Ion-Paired Allylic Lithium Compounds:  Isolation of Inversion Processes

  摘要：

  Among the several ion-ion reorientational processes that take place within several newly studied allylic Lithium compounds, the dynamics of transfer of TMEDA-coordinated lithium between the two allyl faces has been determined independently by use of C-13 NMR line shape studies of diastereotopic geminal methylsilyl groups strategically incorporated close to the chiral lithium in the organometallic species. With increasing temperature, the C-13 Shift between these methyls is progressively averaged due to faster rates of lithium transfer (inversion). Typical Delta H-double dagger values of 5-7 kcal.mol(-1) with Delta S-double dagger = ca. -20 eu are encountered. A faster process, the reorientation of coordinated TMEDA on one side of the allyl plane, has been monitored from the NCH3 C-13 resonance of TMEDA-coordinated Li+, with Delta H-double dagger = 7 kcal.mol(-1) and Delta S-double dagger = ca. -12 eu.

  DOI：

  10.1021/jo982196f

文献信息

• Reorientation Dynamics within Ion-Paired Allylic Lithium Compounds:  Isolation of Inversion Processes
  作者：Gideon Fraenkel、Jose Cabral、Carolina Lanter、Jinhai Wang

  DOI：10.1021/jo982196f

  日期：1999.2.1

  Among the several ion-ion reorientational processes that take place within several newly studied allylic Lithium compounds, the dynamics of transfer of TMEDA-coordinated lithium between the two allyl faces has been determined independently by use of C-13 NMR line shape studies of diastereotopic geminal methylsilyl groups strategically incorporated close to the chiral lithium in the organometallic species. With increasing temperature, the C-13 Shift between these methyls is progressively averaged due to faster rates of lithium transfer (inversion). Typical Delta H-double dagger values of 5-7 kcal.mol(-1) with Delta S-double dagger = ca. -20 eu are encountered. A faster process, the reorientation of coordinated TMEDA on one side of the allyl plane, has been monitored from the NCH3 C-13 resonance of TMEDA-coordinated Li+, with Delta H-double dagger = 7 kcal.mol(-1) and Delta S-double dagger = ca. -12 eu.