N-hydroxy-2-pyridinethione ester of cubylacetic acid | 135191-76-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: N-hydroxy-2-pyridinethione ester of cubylacetic acid
• 英文别名: 1-<<(cubylmethyl)carbonyl>oxy>-2(1H)-pyridinethione；Pentacyclo[4.2.0.02,5.03,8.04,7]octane-1-acetic acid, 2-thioxo-1(2H)-pyridinyl ester；(2-sulfanylidenepyridin-1-yl) 2-cuban-1-ylacetate
• CAS: 135191-76-3
• 化学式: C₁₅H₁₃NO₂S
• 分子量: 271.34
• InChiKey: VDWGCCVWIOFFRH-UHFFFAOYSA-N

物化性质

• 沸点：
  391.5±25.0 °C(Predicted)
• 密度：
  1.60±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.93
• 重原子数：
  19.0
• 可旋转键数：
  3.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  31.23
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  N-hydroxy-2-pyridinethione ester of cubylacetic acid 在 苯硒酚 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 生成 7-Methylene-tricyclo[4.2.0.02,5]oct-3-ene 、 3-Methyl-tricyclo[4.2.0.02,5]octa-3,7-diene
  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-立方烷羰基氯化物 在 4-二甲氨基吡啶 、 草酰氯 、 水 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 20.17h， 生成 N-hydroxy-2-pyridinethione ester of cubylacetic acid
  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

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