1,4-bis(bromomethyl)cubane | 135191-74-1

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 卤代烷
• 英文名称: 1,4-bis(bromomethyl)cubane
• 英文别名: (1s,2R,3r,8S)-1,4-bis(bromomethyl)cubane
• CAS: 135191-74-1
• 化学式: C₁₀H₁₀Br₂
• 分子量: 289.997
• InChiKey: VAZXQBFYTZQZLX-UHFFFAOYSA-N

物化性质

• 沸点：
  304.7±15.0 °C(Predicted)
• 密度：
  2.338±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  12
• 可旋转键数：
  2
• 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：

  1,4-bis(bromomethyl)cubane 在 偶氮二异丁腈 、 三苯基氢化锡 作用下， 以 苯 为溶剂， 反应 0.75h， 以21%的产率得到4,4'-bis(methylenecyclobutene)
  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：

  endo-2,4-dibromodicyclopentadiene-1,8-dione bisethylene ketal 在 盐酸 、 lithium aluminium tetrahydride 、 四溴化碳 、 硫酸 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 3.0h， 生成 1,4-bis(bromomethyl)cubane
  参考文献：
  名称：

  古巴人来到南瓜属现场

  摘要：

  Cubane是一种有趣的化学好奇心，它在1960年代初期首次被研究，已经成为一种有价值的结构基序，并且最近涉及许多潜在化合物的结构。制备第一客体超分子客体5并衍生自1,4-二取代古巴部分，并研究其与葫芦巴[ n ] urils（CB n）和环糊精（CD）的结合行为。双咪唑鎓盐5与CB7，CB8和β-CD形成1：1包合物，其缔合常数分别为（6.7±0.5）×10 11 M –1，（1.5±0.2）×10 9 M –1和< 10 2 M –1在水里。还报告了5 @ CB7和5 @ CB8配合物的固态结构。

  DOI：

  10.1021/acs.orglett.7b01029

文献信息

• Synthesis and structures of 1,4-bis(chloromethyl)-and 1,4-bis(bromomethyl)cubanes
  作者：A. V. Shastin、L. B. Romanova、L. T. Eremenko、V. V. Zakharov、G. V. Lagodzinskaya、G. G. Aleksandrov、I. L. Eremenko

  DOI：10.1007/s11172-006-0439-0

  日期：2006.8

  Abstract1,4-Bis(chloromethyl)-and 1,4-bis(bromomethyl)cubanes were synthesized by the reactions of triphenylphosphine with CCl4 and NBS, respectively. The structures of the compounds were studied by X-ray diffraction analysis.

  摘要 通过三苯基膦与四氯化碳和 NBS 的反应分别合成了 1,4-双(氯甲基)-和 1,4-双(溴甲基)立方烷。通过X射线衍射分析研究了化合物的结构。