1-homocubyl bromide | 135191-73-0

• 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: 1-homocubyl bromide
• 英文别名: 1-bromohomocubane；1-Bromopentacyclo[4.3.0.02,5.03,8.04,7]nonane
• CAS: 135191-73-0
• 化学式: C₉H₉Br
• 分子量: 197.074
• InChiKey: BNYMABKIIYMPOD-UHFFFAOYSA-N

物化性质

• 沸点：
  223.2±9.0 °C(Predicted)
• 密度：
  2.122±0.06 g/cm3(Predicted)

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：
  6.0
• sp3杂化的碳原子比例：
  1.0
• 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-homocubyl bromide 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 氘代苯 为溶剂， 反应 0.33h， 生成 五环[4.3.0.02,5.03,8.04,7]壬烷
  参考文献：
  名称：

  The preparation and fate of cubylcarbinyl radicals

  摘要：

  The cubylcarbinyl radical has been generated from cubylcarbinyl bromide and from the N-hydroxy-2-pyridinethione ester of cubylacetic acid under various conditions favoring hydrogen-atom transfer to the radical. Only when selenophenol in high concentration is used as the hydrogen donor is any methylcubane formed. Otherwise the cubylcarbinyl radical rearranges. There is no evidence of a 1,2-shift into the homocubyl system. Instead, one, two, or three bonds of the cubane nucleus cleave, leading to a variety of olefinic products. For the most part, these have been characterized. A mechanistic scheme accounting for their formation is presented; sequential sigma-bond breaking occurs regioselectively, favoring processes in which there is good overlap between the radical orbital and that of the breaking bond. The distribution of products is shown to depend qualitatively on the time the radical intermediates are let live, that is, on the concentration and effectiveness of the hydrogen atom transfer agent. From product distributions, the rate constant for ring cleavage of cubylcarbinyl radical is calculated to be at least 2 X 10(10) s-1, substantially greater than that of any radical derived to date from a saturated hydrocarbon system. Methodology is given for the synthesis of cubylcarbinol, cubylacetic acid, 1,4-bis(hydroxymethyl)cubane, methylcubane, and a variety of other new cubane compounds.

  DOI：

  10.1021/ja00020a035
• 作为产物：
  描述：

  1-homocubyl cation 在 1-溴金刚烷 作用下， 生成 1-homocubyl bromide
  参考文献：
  名称：

  桥头碳正离子的气相稳定性与溶剂分解速率和 ab 初始计算的相关性

  摘要：

  桥头碳正离子的稳定性已通过基于溴化物和醇的解离质子附着 (DPA) 的傅立叶变换离子回旋共振光谱 (FT ICR) 确定。离子的稳定性与桥头衍生物在 23 log 单位速率范围内的溶剂分解反应性相关，并且与桥头烃在 MP2/6-311G** 水平上的氢化物转移的理论计算相关。

  DOI：

  10.1021/ja962319i