2,2,2-Trifluoro-ethanesulfonic acid 3,3-dimethyl-2-thioxo-bicyclo[3.2.2]non-1-yl ester | 176724-23-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: 2,2,2-Trifluoro-ethanesulfonic acid 3,3-dimethyl-2-thioxo-bicyclo[3.2.2]non-1-yl ester
• 英文别名: (3,3-Dimethyl-2-sulfanylidene-1-bicyclo[3.2.2]nonanyl) 2,2,2-trifluoroethanesulfonate；(3,3-dimethyl-2-sulfanylidene-1-bicyclo[3.2.2]nonanyl) 2,2,2-trifluoroethanesulfonate
• CAS: 176724-23-5
• 化学式: C₁₃H₁₉F₃O₃S₂
• 分子量: 344.419
• InChiKey: SMMCSTHVWHGZMY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  83.8
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2,2,2-Trifluoro-ethanesulfonic acid 3,3-dimethyl-2-thioxo-bicyclo[3.2.2]non-1-yl ester 在 2,6-二甲基吡啶 作用下， 以 乙醇 为溶剂， 反应 40.6h， 生成 2,2-Diethoxy-3,3-dimethyl-bicyclo[3.2.2]nonane-1-thiol 、 1-Mercapto-3,3-dimethyl-bicyclo[3.2.2]nonan-2-one 、 2,2-Dimethyl-bicyclo[2.2.2]octane-1-carbothioic acid O-ethyl ester 、 1-Ethoxy-3,3-dimethyl-bicyclo[3.2.2]nonane-2-thione
  参考文献：
  名称：

  Solvolysis of 2-Thioxo Bicyclic Bridgehead Derivatives:  Evaluation of π-Conjugative Stabilization of α-Thiocarbonyl Carbocations

  摘要：

  The ethanolysis rates of 3,3-dimethyl-2-thioxobicyclo[2.2.2]oct-1 triflate and 3,3-dimethyl-2-thioxobicyclo[3.2.2]non-1-yl triflate relative to their corresponding parent compounds (3,3-dimethylbicyclo[2.2.2]oct-1-yl triflate and 3,3-dimethylbicyclo[3.2.2]non-1-yl triflate, respectively) at 25.0 degrees C increase from 10(-6.2) to 10(-2.5). The increase in the rate ratios with the flexibility of the ring system supports the applicability of the authors' methodology to change the conjugative ability of bridgehead carbocations. Formation of 3,3-dimethyl-1,2-epithio-2-ethoxybicyclo[3.2.2]nonane in the ethanolysis of 3,3-dimethyl-2-thioxobicyclo[3.2.2]non-1-yl 2,2,2-trifluoroethanesulfonate indicates cyclization of the intermediate 3,3-dimethyl-2-thioxobicyclo[3.2.2]nonyl cation into an episulfide cation. Computational studies at the HF/6-31G* level indicate that the resonance interaction between the cationic center and the C=S pi system is greater in the 3,3-dimethyl-2-thioxobicyclo[3.2,2]nonyl cation than in the 3,3-dimethyl-2-thioxobicyclo[2.2.2]octyl cation.

  DOI：

  10.1021/jo9719564
• 作为产物：
  描述：

  3,3-dimethyl-2-hydrazonobicyclo[3.2.2]nonan-1-ol 在 吡啶 、 二氯化二硫 、 三乙胺 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 3.5h， 生成 2,2,2-Trifluoro-ethanesulfonic acid 3,3-dimethyl-2-thioxo-bicyclo[3.2.2]non-1-yl ester
  参考文献：
  名称：

  Solvolysis of 2-Thioxo Bicyclic Bridgehead Derivatives:  Evaluation of π-Conjugative Stabilization of α-Thiocarbonyl Carbocations

  摘要：

  The ethanolysis rates of 3,3-dimethyl-2-thioxobicyclo[2.2.2]oct-1 triflate and 3,3-dimethyl-2-thioxobicyclo[3.2.2]non-1-yl triflate relative to their corresponding parent compounds (3,3-dimethylbicyclo[2.2.2]oct-1-yl triflate and 3,3-dimethylbicyclo[3.2.2]non-1-yl triflate, respectively) at 25.0 degrees C increase from 10(-6.2) to 10(-2.5). The increase in the rate ratios with the flexibility of the ring system supports the applicability of the authors' methodology to change the conjugative ability of bridgehead carbocations. Formation of 3,3-dimethyl-1,2-epithio-2-ethoxybicyclo[3.2.2]nonane in the ethanolysis of 3,3-dimethyl-2-thioxobicyclo[3.2.2]non-1-yl 2,2,2-trifluoroethanesulfonate indicates cyclization of the intermediate 3,3-dimethyl-2-thioxobicyclo[3.2.2]nonyl cation into an episulfide cation. Computational studies at the HF/6-31G* level indicate that the resonance interaction between the cationic center and the C=S pi system is greater in the 3,3-dimethyl-2-thioxobicyclo[3.2,2]nonyl cation than in the 3,3-dimethyl-2-thioxobicyclo[2.2.2]octyl cation.

  DOI：

  10.1021/jo9719564

文献信息

• Solvolysis of 2-thioxo bridgehead compounds as compared with their 2-oxo homologs: Evidence for marked π-conjugation in 2-thioxo carbocation
  作者：Kazuhiko Tokunaga、Yasushi Ohga、Ken'ichi Takeuchi

  DOI：10.1016/0040-4039(96)00265-1

  日期：1996.3

  The solvolysis rate ratios of 2-thioxo bicyclic bridgehead compounds relative to the parent compounds increase with flexibility of the ring system, supporting the propriety of the authors' methodology for evaluation of the enhancement of π-conjugation with increasing skeletal flexibility. On the basis of the fact that no appreciable stabilization due to carbonyl conjugation has been detected by this

  2-硫代双环桥头化合物相对于母体化合物的溶剂分解速率比随环系统的柔性而增加，这支持了作者评估π缀合随骨架柔韧性增强的方法的适当性。基于尚未通过这种方法检测到由于羰基共轭引起的明显的稳定这一事实，叔α-羰基阳离子中的羰基π共轭（如果存在）太小而无法通过实验检测。
• Solvolysis of 2-Thioxo Bicyclic Bridgehead Derivatives:  Evaluation of π-Conjugative Stabilization of α-Thiocarbonyl Carbocations
  作者：Kazuhiko Tokunaga、Takafumi Ohtsu、Yasushi Ohga、Ken'ichi Takeuchi

  DOI：10.1021/jo9719564

  日期：1998.4.1

  The ethanolysis rates of 3,3-dimethyl-2-thioxobicyclo[2.2.2]oct-1 triflate and 3,3-dimethyl-2-thioxobicyclo[3.2.2]non-1-yl triflate relative to their corresponding parent compounds (3,3-dimethylbicyclo[2.2.2]oct-1-yl triflate and 3,3-dimethylbicyclo[3.2.2]non-1-yl triflate, respectively) at 25.0 degrees C increase from 10(-6.2) to 10(-2.5). The increase in the rate ratios with the flexibility of the ring system supports the applicability of the authors' methodology to change the conjugative ability of bridgehead carbocations. Formation of 3,3-dimethyl-1,2-epithio-2-ethoxybicyclo[3.2.2]nonane in the ethanolysis of 3,3-dimethyl-2-thioxobicyclo[3.2.2]non-1-yl 2,2,2-trifluoroethanesulfonate indicates cyclization of the intermediate 3,3-dimethyl-2-thioxobicyclo[3.2.2]nonyl cation into an episulfide cation. Computational studies at the HF/6-31G* level indicate that the resonance interaction between the cationic center and the C=S pi system is greater in the 3,3-dimethyl-2-thioxobicyclo[3.2,2]nonyl cation than in the 3,3-dimethyl-2-thioxobicyclo[2.2.2]octyl cation.