3-(4-Trifluoromethylphenyl)-3-trimethylsilylcyclopropene | 235092-52-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-(4-Trifluoromethylphenyl)-3-trimethylsilylcyclopropene
• 英文别名: Trimethyl-[1-[4-(trifluoromethyl)phenyl]cycloprop-2-en-1-yl]silane
• CAS: 235092-52-1
• 化学式: C₁₃H₁₅F₃Si
• 分子量: 256.343
• InChiKey: RIFSBCXVLRJRBU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.39
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-(4-Trifluoromethylphenyl)-3-trimethylsilylcyclopropene 在 四氟化碳 作用下， 生成
  参考文献：
  名称：

  3-芳基取代的环丙烯基阴离子的重排和3-（4-甲基苯基）环丙烯的气相酸度。

  摘要：

  3-（4-甲基苯基）-3-三甲基甲硅烷基环丙烯和3-（4-三氟甲基苯基）-3-三甲基甲硅烷基环丙烯在气相中与氟离子反应，通过其相应的环丙烯基阴离子的自发重排得到6-取代的3-茚基阴离子。这些异构化导致我们重新研究了所报告的1,2,3-三苯基环丙烯基阴离子的气相生成，并且与先前的研究相反，观察到与1,2-二苯基-1-茚基阴离子相似的重排。尽管3-芳基-3-环丙烯基阴离子的不稳定性，我们仍能够测量烯丙基位置的3-（4-甲基苯基）环丙烯的酸度（δH（o）酸= 398.6 +/- 1.4 kcal / mol）通过DePuy动力学方法。还提出了对单和三芳基取代的环丙烯基阴离子的结构和能量的从头算。

  DOI：

  10.1021/jo001102a
• 作为产物：
  描述：

  3-(4-Trifluoromethylphenyl)-1,2,3-tris(trimethylsilyl)cyclopropene 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 0.33h， 以70%的产率得到3-(4-Trifluoromethylphenyl)-3-trimethylsilylcyclopropene
  参考文献：
  名称：

  Synthesis of 3-aryl-3-trimethylsilylcyclopropenes and their dibenzoyl derivatives. Possible cyclopropenyl anion precursors? †

  摘要：

  3-Ary-1-3-trimethylsilylcyclopropenes (1) were synthesized by a four-step reaction sequence starting from known benzoyl trimethylsilanes. These cyclopropenes were thermalized on a gas chromatography column and the products were collected and identified. Their 1,2-dibenzoyl derivatives (2) were prepared in a two-step transformation beginning with 3-aryl-1,2,3-tris(trimethylsilyl)cyclopropenes (5), the ultimate intermediates in the syntheses of 1. These compounds (2) are rare examples of isolable cyclopropenes with electron withdrawing groups at the vinyl positions. Fluoride-induced desilylation reactions of electron deficient cyclopropenes also are described and a carbon-centered electrophile has been successfully used to trap a putative cyclopropenyl anion.

  DOI：

  10.1039/a900376b

文献信息

• Synthesis of 3-aryl-3-trimethylsilylcyclopropenes and their dibenzoyl derivatives. Possible cyclopropenyl anion precursors? †
  作者：Sangdon Han、Steven R. Kass

  DOI：10.1039/a900376b

  日期：——

  3-Ary-1-3-trimethylsilylcyclopropenes (1) were synthesized by a four-step reaction sequence starting from known benzoyl trimethylsilanes. These cyclopropenes were thermalized on a gas chromatography column and the products were collected and identified. Their 1,2-dibenzoyl derivatives (2) were prepared in a two-step transformation beginning with 3-aryl-1,2,3-tris(trimethylsilyl)cyclopropenes (5), the ultimate intermediates in the syntheses of 1. These compounds (2) are rare examples of isolable cyclopropenes with electron withdrawing groups at the vinyl positions. Fluoride-induced desilylation reactions of electron deficient cyclopropenes also are described and a carbon-centered electrophile has been successfully used to trap a putative cyclopropenyl anion.
• Rearrangements of 3-Aryl-Substituted Cyclopropenyl Anions and the Gas-Phase Acidity of 3-(4-Methylphenyl)cyclopropene
  作者：Katherine M. Broadus、Sangdon Han、Steven R. Kass

  DOI：10.1021/jo001102a

  日期：2001.1.1

  6-substituted 3-indenyl anions via a spontaneous rearrangement of their corresponding cyclopropenyl anions. These isomerizations led us to reinvestigate the reported gas-phase generation of 1,2,3-triphenylcyclopropenyl anion, and contrary to the previous study, a similar rearrangement to 1,2-diphenyl-1-indenyl anion is observed. Despite the instability of 3-aryl-3-cyclopropenyl anions, we were able to measure

  3-（4-甲基苯基）-3-三甲基甲硅烷基环丙烯和3-（4-三氟甲基苯基）-3-三甲基甲硅烷基环丙烯在气相中与氟离子反应，通过其相应的环丙烯基阴离子的自发重排得到6-取代的3-茚基阴离子。这些异构化导致我们重新研究了所报告的1,2,3-三苯基环丙烯基阴离子的气相生成，并且与先前的研究相反，观察到与1,2-二苯基-1-茚基阴离子相似的重排。尽管3-芳基-3-环丙烯基阴离子的不稳定性，我们仍能够测量烯丙基位置的3-（4-甲基苯基）环丙烯的酸度（δH（o）酸= 398.6 +/- 1.4 kcal / mol）通过DePuy动力学方法。还提出了对单和三芳基取代的环丙烯基阴离子的结构和能量的从头算。