2-trimethylsilyl-4-methoxyacetanilide | 944583-29-3

• 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: 2-trimethylsilyl-4-methoxyacetanilide
• 英文别名: N-(4-methoxy-2-trimethylsilylphenyl)acetamide
• CAS: 944583-29-3
• 化学式: C₁₂H₁₉NO₂Si
• 分子量: 237.374
• InChiKey: BWQGDKAZZLKHCR-UHFFFAOYSA-N

物化性质

• 沸点：
  347.9±37.0 °C(Predicted)
• 密度：
  1.01±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-溴-4-甲氧基苯酚 在 吡啶 、 正丁基锂 、 水 、 丙酮 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 29.8h， 生成 2-trimethylsilyl-4-methoxyacetanilide 、 3-三甲基硅烷基苯甲醚
  参考文献：
  名称：

  探索离去基团对苯基阳离子的产生和反应性的影响

  摘要：

  苯阳离子是通过Ar-LG键（LG =离开基团）的光解裂解而平稳生成的。为了评估该方法的范围，提出了一系列4-甲氧基-2-（三甲基甲硅烷基）苯基衍生物（磺酸，LG = MeSO 3和CF 3 SO 3，磷酸盐，LG =（EtO）2（O）PO酯和相应的氯化物）已作为比较探针，用于评估离去基团的能力。光裂解是一个普遍的反应，（EtO）2（O）PO〜Cl > CF 3 SO 3 > MeSO 3（CF 3 CH 2 OH中的Φ= 0.50至0.16，而MeCN–H中的值较低）2 O）。随之而来的反应并不取决于LG，而仅取决于苯基阳离子的结构（甲硅烷基将三重态调节为单重态系统间穿越和亲电性）和介质（与水形成络合物会减慢亲电反应）。

  DOI：

  10.1021/jo300290v

文献信息

• The β Effect of Silicon in Phenyl Cations
  作者：Valentina Dichiarante、Andrea Salvaneschi、Stefano Protti、Daniele Dondi、Maurizio Fagnoni、Angelo Albini

  DOI：10.1021/ja074778x

  日期：2007.12.1

  Irradiation of chloroanisoles, phenols, and N,N-dimethylanilines bearing a trimethylsilyl (TMS) group in the ortho position with respect to the chlorine atom caused photoheterolysis of the Ar-Cl bond and formation of the corresponding ortho-trimethylsilylphenyl cations in the triplet state. The beta effect of silicon on these intermediates has been studied by comparing the resulting chemistry in alcoholic solvents with that of the silicon-free analogues and by computational analysis (at the UB3LYP/6-311+G(2d,p) level in MeOH). TMS groups little affect the photophysics and the photocleavage of the starting phenyl chlorides, while stabilizing the phenyl cations, both in the triplet (ca. 4 kcal/mol per group) and, dramatically, in the singlet state (9 kcal/mol). As a result, although triplet phenyl cations are the first formed species, intersystem crossing to the more stable singlets is favored with chloroanisoles and phenols. Indeed, with these compounds, solvent addition to give aryl ethers (from the singlet) competed efficiently with reduction or arylation (from the triplet). In the case of the silylated 4-chloro-NN-dimethylaniline, the triplet cation remained in the ground state and trapping by pi nucleophiles remained efficient, though slowed by the steric bulk of the TMS group. In alcohols, the silyl group was eliminated via a photoinduced protiodesilylation during the irradiation. Thus, the silyl group could be considered as a directing, photoremovable group that allowed shifting to the singlet phenyl cation chemistry and was smoothly eliminated in the same one-pot procedure.