(4-[(trimethylsilyl)methyl]phenyl)methyl acetate | 875556-32-4

• 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: (4-[(trimethylsilyl)methyl]phenyl)methyl acetate
• 英文别名: [p-((trimethylsilyl)methyl)phenyl]methyl acetate；Acetic acid 4-trimethylsilanylmethylbenzyl ester；[4-(trimethylsilylmethyl)phenyl]methyl acetate
• CAS: 875556-32-4
• 化学式: C₁₃H₂₀O₂Si
• 分子量: 236.386
• InChiKey: STOAPSWKXPUWCZ-UHFFFAOYSA-N

物化性质

• 沸点：
  282.0±20.0 °C(Predicted)
• 密度：
  0.969±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.17
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (4-[(trimethylsilyl)methyl]phenyl)methyl acetate 在 四丁基氟化铵 作用下， 以 氘代乙腈 为溶剂， 反应 0.25h， 生成 对二甲苯二聚体
  参考文献：
  名称：

  Room Temperature Observation of p-Xylylenes by ¹H NMR and Evidence for Diradical Intermediates in Their Oligomerization

  摘要：

  p-Quinodimethanes (p-QDMs) are reactive molecules that have been invoked as transient intermediates in a number of reactions. Dilute solutions of benzene-based p-QDMs, p-xylylene (1), a-methyl-p-xylylene (10), and 2,5-dimethyl-p-xylylene (11) can be prepared by fluoride-induced elimination of trimethylsilyl acetate from the appropriate precursor. It has been found that these solutions are stable enough to allow these reactive p-QDMs to be observed by H-1 NMR spectroscopy at room temperature. For the first time, the 13 C NMR spectrum of p-QDM 1 was observed. After several hours at room temperature, these p-QDMs form dimers, trimers, and insoluble oligomers. Formation of trimers provides evidence that p-QDMs 1, 10, and 11 dimerize by a stepwise mechanism involving dimeric diradicals as intermediates.

  DOI：

  10.1021/jo0516279
• 作为产物：
  描述：

  4-((三甲基甲硅烷基)甲基)苯甲酸 在 吡啶 、 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 0.25h， 生成 (4-[(trimethylsilyl)methyl]phenyl)methyl acetate
  参考文献：
  名称：

  Room Temperature Observation of p-Xylylenes by ¹H NMR and Evidence for Diradical Intermediates in Their Oligomerization

  摘要：

  p-Quinodimethanes (p-QDMs) are reactive molecules that have been invoked as transient intermediates in a number of reactions. Dilute solutions of benzene-based p-QDMs, p-xylylene (1), a-methyl-p-xylylene (10), and 2,5-dimethyl-p-xylylene (11) can be prepared by fluoride-induced elimination of trimethylsilyl acetate from the appropriate precursor. It has been found that these solutions are stable enough to allow these reactive p-QDMs to be observed by H-1 NMR spectroscopy at room temperature. For the first time, the 13 C NMR spectrum of p-QDM 1 was observed. After several hours at room temperature, these p-QDMs form dimers, trimers, and insoluble oligomers. Formation of trimers provides evidence that p-QDMs 1, 10, and 11 dimerize by a stepwise mechanism involving dimeric diradicals as intermediates.

  DOI：

  10.1021/jo0516279

文献信息

• Computational and Experimental Confirmation of the Diradical Character of <i>para</i>-Quinonedimethide
  作者：Zhipeng Pei、Nicholas L. Magann、Madison J. Sowden、Rhys B. Murphy、Michael G. Gardiner、Michael S. Sherburn、Michelle L. Coote

  DOI：10.1021/jacs.3c04363

  日期：2023.7.26

  para-quinonedimethide (p-QDM) molecule is generally represented in its closed shell form, i.e., as a cyclic, nonaromatic, through-conjugated/cross-conjugated hybrid comprising four C═C bonds. Nonetheless, p-QDM has been theorized to contain a contribution from its open-shell aromatic singlet diradical form. VBSCF calculations identify an open-shell contribution of 29% to the structure, while CASPT2(16,16)/def2-TZVP

  母体对醌二甲基化物( p -QDM)分子的基态结构通常以其闭壳形式表示，即作为包含四个C=C键的环状、非芳香族、直通共轭/交叉共轭杂化物。尽管如此，p -QDM 已被理论化为包含其开壳芳香族单线态双自由基形式的贡献。VBSCF 计算确定开壳层对结构的贡献为 29%，而 CASPT2(16,16)/def2-TZVP 和 ωB97XD/aug- cc -pVTZ 计算预测二聚化沿着开壳层单线态双自由基途径进行，具有较低的(77 kJ/mol) 二聚化障碍，二聚化是通过环外亚甲基碳之间形成 C-C 键而发生的。p -QDM 分子与自由基陷阱 TEMPO之间的反应也存在类似的低势垒 (98 kJ/mol) 。这些预测通过分离双-TEMPO 捕获的p -QDM（其 C-C 偶联二聚体）以及通过证明p -QDM 和 TEMPO的混合物可以在环境温度下引发丙烯酸正丁酯的自由基聚合而得到实验验证。 。与p
• Synthesis of Functionalized Benzylsilanes from Arylzinc Compounds and (Iodomethyl)trimethylsilane by Means of a Novel Rh Catalysis
  作者：Hideki Takahashi、Kabir M. Hossain、Yasushi Nishihara、Takanori Shibata、Kentaro Takagi

  DOI：10.1021/jo0520994

  日期：2006.1.1

  [GRAPHICS]The catalytic activity of a Rh complex in cross-coupling between ArZnI and TMSCH2I was examined in which the Rh complex, generated in situ from [RhCl(1,5-cyclooctadiene)](2) and 1,1'-bis(diphenylphosphino)ferrocene, exhibited excellent catalytic activity for the production of various functionalized benzylsilanes in good yields. From P-31 NMR studies of various solutions containing several of the reaction components, confirmation of the rapid and quantitative transfer of aryl groups from ArZnI to the Rh complex to form arylrhodium species was ascertained. A catalytic cycle, commencing with the transmetalation, was thus proposed for the reaction.