(3Z,5Z)-1-bromo-3,5-octadiene | 179331-80-7

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机溴化物
• 英文名称: (3Z,5Z)-1-bromo-3,5-octadiene
• 英文别名: (3Z,5Z)-1-bromoocta-3,5-diene
• CAS: 179331-80-7
• 化学式: C₈H₁₃Br
• 分子量: 189.095
• InChiKey: FTGDDWLXEDEMCF-OUPQRBNQSA-N

物化性质

• 沸点：
  210.9±9.0 °C(Predicted)
• 密度：
  1.174±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  9
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  (3Z,5Z)-1-bromo-3,5-octadiene 在 dilithium tetrachlorocuprate 、 三氯化铁 、 magnesium 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 生成 (E,Z)-7,9-dodecadienyl acetate
  参考文献：
  名称：

  Synthesis of (7Z,9Z)-dodecadienyi acetate, a component of sex pheromones of the leafrollersEpinotia andEucosma, using conjugated diynols

  摘要：

  Two analogous routes to the title pheromones were elaborated based on organocuprate cross-coupling of Z,Z-dienic electrophiles, (2Z,4Z)-1-acetoxy-2,4-heptadiene (6) and (3Z,5Z)-1-bromoctadiene (8), with omega-tert-butoxy-1-chloropentane and -butane, respectively. Optimal conditions for the reduction of 2,4-heptadiyn-1-ol and 3,5-octadiyn-1-ol to the respective Z,Z-alkadienols as precursors for the electrophiles were found. Treatment of diynols with activated zinc in aqueous alcohol provided high geometrical purity of the product (greater-than-or-equal-to 94 %). In both cases, copper-catalyzed cross-coupling afforded 1-tert-butoxy-7,9-dodecadiene (four stereoisomers), acetolysis of which gave the target pheromone contaminated by stereoisomers. In the case of allylic electrophile 6, the reaction occurred with the loss of the initial configurational purity, whereas the use of homoallylic bromide 8 ensured almost complete retention of the configuration of the double bonds and obtaining the target pheromone of 87 % configurational purity.

  DOI：

  10.1007/bf00699203
• 作为产物：
  描述：

  3,5-octadiyn-1-ol 在 氢氧化钾 、 锌铜偶 、 lithium bromide 作用下， 以 乙醚 、 水 、 N,N-二甲基甲酰胺 、 异丙醇 为溶剂， 反应 19.5h， 生成 (3Z,5Z)-1-bromo-3,5-octadiene
  参考文献：
  名称：

  Synthesis of (7Z,9Z)-dodecadienyi acetate, a component of sex pheromones of the leafrollersEpinotia andEucosma, using conjugated diynols

  摘要：

  Two analogous routes to the title pheromones were elaborated based on organocuprate cross-coupling of Z,Z-dienic electrophiles, (2Z,4Z)-1-acetoxy-2,4-heptadiene (6) and (3Z,5Z)-1-bromoctadiene (8), with omega-tert-butoxy-1-chloropentane and -butane, respectively. Optimal conditions for the reduction of 2,4-heptadiyn-1-ol and 3,5-octadiyn-1-ol to the respective Z,Z-alkadienols as precursors for the electrophiles were found. Treatment of diynols with activated zinc in aqueous alcohol provided high geometrical purity of the product (greater-than-or-equal-to 94 %). In both cases, copper-catalyzed cross-coupling afforded 1-tert-butoxy-7,9-dodecadiene (four stereoisomers), acetolysis of which gave the target pheromone contaminated by stereoisomers. In the case of allylic electrophile 6, the reaction occurred with the loss of the initial configurational purity, whereas the use of homoallylic bromide 8 ensured almost complete retention of the configuration of the double bonds and obtaining the target pheromone of 87 % configurational purity.

  DOI：

  10.1007/bf00699203

文献信息

• US7655253B2
  申请人：——

  公开号：US7655253B2

  公开（公告）日：2010-02-02
• Synthesis of (7Z,9Z)-dodecadienyi acetate, a component of sex pheromones of the leafrollersEpinotia andEucosma, using conjugated diynols
  作者：Z. G. Chrelashvili、M. V. Mavrov、B. I. Ugrak、A. A. Kutin、E. P. Serebryakov

  DOI：10.1007/bf00699203

  日期：1993.9

  Two analogous routes to the title pheromones were elaborated based on organocuprate cross-coupling of Z,Z-dienic electrophiles, (2Z,4Z)-1-acetoxy-2,4-heptadiene (6) and (3Z,5Z)-1-bromoctadiene (8), with omega-tert-butoxy-1-chloropentane and -butane, respectively. Optimal conditions for the reduction of 2,4-heptadiyn-1-ol and 3,5-octadiyn-1-ol to the respective Z,Z-alkadienols as precursors for the electrophiles were found. Treatment of diynols with activated zinc in aqueous alcohol provided high geometrical purity of the product (greater-than-or-equal-to 94 %). In both cases, copper-catalyzed cross-coupling afforded 1-tert-butoxy-7,9-dodecadiene (four stereoisomers), acetolysis of which gave the target pheromone contaminated by stereoisomers. In the case of allylic electrophile 6, the reaction occurred with the loss of the initial configurational purity, whereas the use of homoallylic bromide 8 ensured almost complete retention of the configuration of the double bonds and obtaining the target pheromone of 87 % configurational purity.