(Z,Z)-1-Bromo-1,4-heptadiene | 150698-30-9

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 英文名称: (Z,Z)-1-Bromo-1,4-heptadiene
• 英文别名: (1Z,4Z)-1-bromohepta-1,4-diene
• CAS: 150698-30-9
• 化学式: C₇H₁₁Br
• 分子量: 175.068
• InChiKey: MDDBMSOWKXNKLF-CWWKMNTPSA-N

物化性质

• 沸点：
  162.4±19.0 °C(Predicted)
• 密度：
  1.211±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  8
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.43
• 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：

  (Z,Z)-1-Bromo-1,4-heptadiene 、 (2R,3R)-2-iodomethyl-3-nonyloxirane 在 magnesium 、 1,2-二溴乙烷 、 copper(l) iodide 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 为溶剂， 反应 1.5h， 以39%的产率得到(2R,3S)-2-nonyl-3-((2Z,5Z)-octa-2,5-dienyl)oxirane
  参考文献：
  名称：

  Improved Synthesis and Deployment of (2S,3R)-2-(2Z,5Z-Octadienyl)-3-nonyloxirane, a Pheromone of the Pink Moth, Lymantria mathura

  摘要：

  We report two new syntheses of (2S,3R)-2-(2Z5Z-octadienyl)-3-nonyloxirane, the main sex pheromone component of the pink moth, Lymantria mathura. The key step in the first route was the construction of (Z,Z)-1-bromo-1,4-heptadiene (6), which was coupled in the final step with 2-iodomethyl-3-nonyloxirane 4 via a Grignard reaction. The second approach employed alkylation of 1,4-heptadiynyllithium with epoxy triflates 7 in ether/hexane and provided the pheromone in greater than or equal to37% overall yield from alcohol 2. The 4:1 ratio of pheromone enantiomers, reportedly the most attractive to pink moth males, can be directly crafted from appropriately selected Sharpless asymmetric epoxidation conditions.

  DOI：

  10.1021/jf035506q
• 作为产物：
  描述：

  1,4-庚二炔 在 N-溴代丁二酰亚胺(NBS) 、 (Sia)2BH 、 silver nitrate 、 溶剂黄146 作用下， 以 丙酮 为溶剂， 反应 21.75h， 生成 (Z,Z)-1-Bromo-1,4-heptadiene
  参考文献：
  名称：

  Alkylative epoxide rearrangement. A stereospecific approach to chiral epoxide pheromones

  摘要：

  The alkylative rearrangement of 1,2-epoxy-3-alkanol tosylates is applied to the synthesis of chiral epoxide pheromones. Attack at the terminal carbon atom of epoxy tosylates by lithioacetylenes and cyclization of the intermediate tosyloxy alcohols produces internal epoxides in high yield. The method is stereospecific: threo-epoxy tosylates give eL's-epoxides, and erythro-epoxy tosylates yield trans-epoxides. Several diastereomerically pure epoxides were prepared in high optical purity from chiral pool intermediates derived from sugars. Pheromone components prepared include (+/-)-cis-epoxyalkene 20 and both enantiomers of cis-epoxy diene 16, a female sex pheromone component of a number of lepidopteran species. These results demonstrate that alkylative rearrangement of 1,2-epoxy-3-alkanol tosylates complements existing methods for stereoselective synthesis of epoxides, including the Payne rearrangement and Sharpless epoxidation.

  DOI：

  10.1021/jo00071a026

文献信息

• Improved Synthesis and Deployment of (2<i>S</i>,3<i>R</i>)-2-(2<i>Z</i>,5<i>Z</i>-Octadienyl)-3-nonyloxirane, a Pheromone of the Pink Moth, <i>Lymantria mathura</i>
  作者：Ashot Khrimian、James E. Oliver、Roger C. Hahn、Nikki H. Dees、Jeff White、Victor C. Mastro

  DOI：10.1021/jf035506q

  日期：2004.5.1

  We report two new syntheses of (2S,3R)-2-(2Z5Z-octadienyl)-3-nonyloxirane, the main sex pheromone component of the pink moth, Lymantria mathura. The key step in the first route was the construction of (Z,Z)-1-bromo-1,4-heptadiene (6), which was coupled in the final step with 2-iodomethyl-3-nonyloxirane 4 via a Grignard reaction. The second approach employed alkylation of 1,4-heptadiynyllithium with epoxy triflates 7 in ether/hexane and provided the pheromone in greater than or equal to37% overall yield from alcohol 2. The 4:1 ratio of pheromone enantiomers, reportedly the most attractive to pink moth males, can be directly crafted from appropriately selected Sharpless asymmetric epoxidation conditions.
• Alkylative epoxide rearrangement. A stereospecific approach to chiral epoxide pheromones
  作者：Thomas W. Bell、James A. Ciaccio

  DOI：10.1021/jo00071a026

  日期：1993.9

  The alkylative rearrangement of 1,2-epoxy-3-alkanol tosylates is applied to the synthesis of chiral epoxide pheromones. Attack at the terminal carbon atom of epoxy tosylates by lithioacetylenes and cyclization of the intermediate tosyloxy alcohols produces internal epoxides in high yield. The method is stereospecific: threo-epoxy tosylates give eL's-epoxides, and erythro-epoxy tosylates yield trans-epoxides. Several diastereomerically pure epoxides were prepared in high optical purity from chiral pool intermediates derived from sugars. Pheromone components prepared include (+/-)-cis-epoxyalkene 20 and both enantiomers of cis-epoxy diene 16, a female sex pheromone component of a number of lepidopteran species. These results demonstrate that alkylative rearrangement of 1,2-epoxy-3-alkanol tosylates complements existing methods for stereoselective synthesis of epoxides, including the Payne rearrangement and Sharpless epoxidation.