2-(phenylsulfonyl)fluorene | 59014-85-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 2-(phenylsulfonyl)fluorene
• 英文别名: 2-(benzenesulfonyl)-9H-fluorene
• CAS: 59014-85-6
• 化学式: C₁₉H₁₄O₂S
• 分子量: 306.385
• InChiKey: LUPLWIBYVHYKAU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  22
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  42.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(phenylsulfonyl)fluorene 在 N-溴代丁二酰亚胺(NBS) 、 过氧化苯甲酰 作用下， 以 乙醇 、 氯仿 为溶剂， 反应 4.0h， 生成 N-<9-<2-(phenylsulfonyl)fluorenyl>>trimethylammonium bromide
  参考文献：
  名称：

  Equilibrium acidities and homolytic bond dissociation energies of the acidic carbon-hydrogen bonds in N-substituted trimethylammonium and pyridinium cations

  摘要：

  Equilibrium acidities (pK(HA)s) of the cations in sixteen N-substituted trimethylammonium salts, one N-phenacylquinuclidinium salt, eight N-substituted pyridinium salts, and N-(ethoxycarbonyl)isoquinolinium bromide, together with the oxidation potentials of their conjugate bases, have been determined in dimethyl sulfoxide (DMSO) solution. The acidifying effects of the alpha-trimethylammonium groups (alpha-Me3N+) and the alpha-pyridinium groups (alpha-PyN+) on the adjacent acidic C-H bonds in these cations were found to average about 10 and 18 pK(HA) units, respectively, in DMSO. The homolytic bond dissociation energies of the acidic C-H bonds in these cations, estimated by the combination of the equilibrium acidities with the oxidation potentials of their corresponding conjugate bases (ylides), show that the alpha-trimethylammonium groups destabilize adjacent radicals by 2-6 kcal/mol, whereas alpha-pyridinium groups stabilize adjacent radicals by 3-6 kcal/mol. The effects of alpha-pyridinium groups on the stabilization energies of the radicals derived from these cations were found to be ca. 4-10 kcal/mol smaller than those of the corresponding phenyl groups, whereas their effects on the equilibrium acidities of the cations were 5.4-13.1 pK(HA) units larger. The pK(HA) value of tetramethylammonium cation (Me4N+) was estimated by extrapolation to be about 42 in DMSO.

  DOI：

  10.1021/jo00063a026
• 作为产物：
  描述：

  芴 、 苯磺酰氯 在 四氯化锡 作用下， 生成 2-(phenylsulfonyl)fluorene
  参考文献：
  名称：

  Aleykutty; Baliah, Journal of the Indian Chemical Society, 1955, vol. 32, p. 702

  摘要：

  DOI：

文献信息

• Standard p<i>K</i>_a Scales of Carbon-Centered Indicator Acids in Ionic Liquids: Effect of Media and Structural Implication
  作者：Hui Deng、Xin Li、Yuan Chu、Jiaqi He、Jin-Pei Cheng

  DOI：10.1021/jo300941g

  日期：2012.9.7

  Here we describe a general approach to measure absolute pKa’s in pure ionic liquid (IL). The standard conditions warranting accurate measurement were outlined. The pKa’s of the selected 18 C–H type indicator acids in four ILs were determined and a convenient indicator platform was constructed for easy expansion of acidity scales. These absolute pKa’s make possible, for the first time, direct comparisons

  键解离的能量学，尤其是R–H键杂合自由能（p K a），在促进化学成为一门科学方面发挥了核心作用。尽管在文献中对酸度进行了研究，但目前的知识仅限于经典分子溶剂中的知识，并且无法扩展以预测离子介质中酸度的变化。由于后者现在非常流行于替代挥发性有机溶剂，因此迫切需要了解随着介质组成从中性分子转换为带电离子而改变键裂解的驱动力的方法。在这里，我们描述了一种测量绝对值p K a的通用方法在纯离子液体（IL）中。概述了保证精确测量的标准条件。确定了四个IL中所选的18 C–H型指示剂酸的p K a，并构建了方便的指示剂平台以轻松扩展酸度标度。这些绝对的p K a使得首次可以将IL中的键能与分子溶剂中以及气相中的键能进行直接比较，并且应该能够用作校准适合于该研究的计算方法的标准参数。在离子介质中。分析了IL中阳离子和阴离子与结构的关系。