1,1-dibromo-6-chloro-3-ethyl-1-hexene | 138541-98-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,1-dibromo-6-chloro-3-ethyl-1-hexene
• 英文别名: 1,1-Dibromo-6-chloro-3-ethylhex-1-ene
• CAS: 138541-98-7
• 化学式: C₈H₁₃Br₂Cl
• 分子量: 304.452
• InChiKey: CYAZGMVODQPADB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  1,1-dibromo-6-chloro-3-ethyl-1-hexene 在 正丁基锂 、 sodium iodide 作用下， 以 四氢呋喃 、 丙酮 为溶剂， 反应 16.5h， 生成 6-iodo-3-ethyl-1-hexyne
  参考文献：
  名称：

  Stereochemistry of metal-halogen exchange-initiated intramolecular conjugate addition reactions in the construction of 5-membered carbocycles

  摘要：

  The stereochemistry of some lithium-iodine exchange-initiated cyclization reactions of model omega-iodo, gamma-substituted activated olefins has been studied. The stereoselectivities of these anionic cyclization reactions have been found to be a function of the olefin activator employed, reaction conditions, Michael acceptor olefin geometry, the nature of the gamma-substituent, and, in some cases, the presence of additives. Cyclization reactions of iodides possessing E olefin geometry give a moderate preference for trans cyclopentane formation while Z olefin geometry leads to extremely high (> 300:1) trans product selectivity. Cyclization reactions of E olefins under radical conditions were found to be slightly more trans-selective than those observed under anionic conditions although Z olefin geometry again promotes very high trans product selectivity. The presence of the allylic methoxyl group in (E)-7d leads to cis selectivity under both anionic and radical conditions. Intramolecular complexation involving the reactive carbon center and the methoxyl group is suggested in both modes as a possible explanation for this cis product selectivity.

  DOI：

  10.1021/jo00031a031
• 作为产物：
  描述：

  5-氯戊酸乙酯 在 正丁基锂 、 二异丁基氢化铝 、 二异丙胺 、 三苯基膦 作用下， 以 正己烷 、 甲苯 为溶剂， 反应 15.16h， 生成 1,1-dibromo-6-chloro-3-ethyl-1-hexene
  参考文献：
  名称：

  Stereochemistry of metal-halogen exchange-initiated intramolecular conjugate addition reactions in the construction of 5-membered carbocycles

  摘要：

  The stereochemistry of some lithium-iodine exchange-initiated cyclization reactions of model omega-iodo, gamma-substituted activated olefins has been studied. The stereoselectivities of these anionic cyclization reactions have been found to be a function of the olefin activator employed, reaction conditions, Michael acceptor olefin geometry, the nature of the gamma-substituent, and, in some cases, the presence of additives. Cyclization reactions of iodides possessing E olefin geometry give a moderate preference for trans cyclopentane formation while Z olefin geometry leads to extremely high (> 300:1) trans product selectivity. Cyclization reactions of E olefins under radical conditions were found to be slightly more trans-selective than those observed under anionic conditions although Z olefin geometry again promotes very high trans product selectivity. The presence of the allylic methoxyl group in (E)-7d leads to cis selectivity under both anionic and radical conditions. Intramolecular complexation involving the reactive carbon center and the methoxyl group is suggested in both modes as a possible explanation for this cis product selectivity.

  DOI：

  10.1021/jo00031a031

文献信息

• Metal-halogen exchange-initiated intramolecular conjugate addition reactions of conjugated acetylenic esters
  作者：Manning P. Cooke

  DOI：10.1021/jo00076a053

  日期：1993.11

  The lithium-iodine exchange-initiated intramolecular conjugate addition reactions of some model gamma-iodo-alpha,beta-acetylenic esters have been examined. Product mixtures arising from proton abstraction reactions were observed in reactions leading to 5-membered ring formation. More efficient cyclizations resulted when reactions were conducted in the presence of trimethylsilyl chloride to trap intermediate allenolate ions. Allenolate ion trapping by an internal electrophilic center in 26 resulted in the highly efficient formation of bicyclic ester 27.