cubylcarbinyl radical | 135191-71-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: cubylcarbinyl radical
• CAS: 135191-71-8
• 化学式: C₉H₉
• 分子量: 117.17
• InChiKey: PDNGPWHEWYTNGT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.89
• 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：

  cubylcarbinyl radical 以 various solvent(s) 为溶剂， 生成
  参考文献：
  名称：

  古巴的均裂反应。cubyl 和 cubylcarbinyl 自由基的生成和表征

  摘要：

  通过从 1-bromo-4-取代的立方烷中提取溴原子，产生了一系列 4-取代的立方自由基。EPR 观察表明，cubyl 自由基从三乙基硅烷的乙基中提取二级氢原子，主要通过二级组合反应衰变。在-90 o C 时，叔丁氧基从立方烷中提取氢原子的速度至少比环丙烷快26 倍。立方烷上的吸电子取代基大大降低了这一速度。叔丁氧基自由基选择性地从甲基立方烷中提取笼氢而不是伯甲基氢

  DOI：

  10.1021/ja00053a008

文献信息

• Picosecond radical kinetics. Bond cleavage of the cubylcarbinyl radical
  作者：Seung Yong Choi、Philip E. Eaton、Martin Newcomb、Yu Chi Yip

  DOI：10.1021/ja00042a008

  日期：1992.7

  Rate constants for the initial ond clevages of the cubylcarbinyl radical (1) were determined by competition kinetics using benzeneselenol as a trapping agent. Measurements over the temperature range -78 to 25 o C gave a temperature-dependent function of log (k r .s) = 13.16-3.72/2.3RT. The rate constant for the initial ring opening of radical 1 at 25 o C is 2.9×10 10 s -1 , which ranks this reaction

  cubylcarbinyl 自由基 (1) 的初始和裂解的速率常数是通过使用苯硒醇作为捕获剂的竞争动力学确定的。在 -78 到 25 o C 温度范围内的测量给出了 log (kr .s) = 13.16-3.72/2.3RT 的温度相关函数。自由基 1 在 25 o C 下初始开环的速率常数为 2.9×10 10 s -1 ，这将该反应列为已知最快的自由基重排之一。初始裂解反应的推定产物，亚甲基仲仲基自由基 2，显然经历了更快的键裂解反应，估计在 250 * C 下 >1.5×10 11 s -1
• The preparation and fate of cubylcarbinyl radicals
  作者：Philip E. Eaton、Yu Chi Yip

  DOI：10.1021/ja00020a035

  日期：1991.9

  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.