1,2-dimethyl-4-trimethylsilyloxybenzene | 17994-04-6

• 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: 1,2-dimethyl-4-trimethylsilyloxybenzene
• 英文别名: 1-Trimethylsilyloxy-3,4-dimethyl-benzol；Phenol, 3,4-dimethyl, TMS；(3,4-dimethylphenoxy)-trimethylsilane
• CAS: 17994-04-6
• 化学式: C₁₁H₁₈OSi
• 分子量: 194.349
• InChiKey: HUJKPJDYBJPESM-UHFFFAOYSA-N

物化性质

• 沸点：
  213-215 °C
• 密度：
  0.9294 g/cm3(Temp: 21 °C)
• 保留指数：
  1244;1258

计算性质

• 辛醇/水分配系数(LogP)：
  3.52
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1,2-dimethyl-4-trimethylsilyloxybenzene 在 甲醇 、 1,3-disulfonic acid imidazolium hydrogen sulfate 作用下， 反应 0.08h， 以97%的产率得到3,4-二甲基苯酚
  参考文献：
  名称：

  Preparation, characterization and use of 1,3-disulfonic acid imidazolium hydrogen sulfate as an efficient, halogen-free and reusable ionic liquid catalyst for the trimethylsilyl protection of hydroxyl groups and deprotection of the obtained trimethylsilanes

  摘要：

  Novel 1,3-disulfonic acid imidazolium hydrogen sulfate, a halogen-free ionic liquid, is a recyclable and eco-benign catalyst for the trimethylsilyl protection of hydroxyl groups at room temperature under solvent free conditions to afford trimethylsilanes in excellent yields (92-100%) and in very short reaction times (1-5 min). Deprotection of the resulting trimethylsilanes can also be achieved using the same catalyst in methanol. The catalyst was characterized by IR. H-1 NMR, C-13 NMR and MS studies. All the products were extensively characterized by IR, H-1 NMR, MS, and elemental and melting point analyses. This new method consistently has the advantages of excellent yields and short reaction times. Further, the catalyst can be recovered and reused for several times without loss of activity. The work-up of the reaction consists of a simple separation, followed by concentration of the crude product and purification. (C) 2012 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2012.08.002
• 作为产物：
  描述：

  3,4-二甲基苯酚 生成 1,2-dimethyl-4-trimethylsilyloxybenzene
  参考文献：
  名称：

  LAUTERBUCH, MANFRED;JUGER, GUNTER;JANCKE, HARALD;LEHMANN, ANDREAS;ZIMMERM+, CHEM. TECHN. , 42,(1990) N, C. 264-268

  摘要：

  DOI：

文献信息

• Regioselectivity of Hydroxyl Radical Reactions with Arenes in Nonaqueous Solutions
  作者：Lee C. Moores、Devinder Kaur、Mathew D. Smith、James S. Poole

  DOI：10.1021/acs.joc.8b03188

  日期：2019.3.15

  The regioselectivity of hydroxyl radical addition to arenes was studied using a novel analytical method capable of trapping radicals formed after the first elementary step of reaction, without alteration of the product distributions by secondary oxidation processes. Product analyses of these reactions indicate a preference for o- over p-substitution for electron donating groups, with both favored over

  使用新颖的分析方法研究了羟基自由基在芳烃中的区域选择性，该方法能够捕获在第一步反应后形成的自由基，而不会因二次氧化过程而改变产物的分布。这些反应的产物分析表明为偏好ø -过p 3'-取代为供电子基团，既优于米-添加。尽管观察到的区域选择性的幅度对于羟基更大，但观察到的分布在质量上与添加其他以碳为中心的自由基时观察到的分布相似。通过高精度CBS-QB3计算方法复制的数据表明，极性和自由基稳定化作用均在观察到的区域选择性中起作用。讨论了所用分析方法的应用和潜在局限性。
• Differentiation of isomeric cresols by silylation in combination with gas chromatography/mass spectrometry analysis
  作者：Jiaxiang Xu、Guohua Zhu、Huarong Zhang、Jinsong Liu、Kezhi Jiang

  DOI：10.1002/rcm.8576

  日期：2020.2.15

  accurately determine isomeric cresols due to their incomplete chromatographic separation on commercially available chromatographic columns and their nearly identical mass spectra. METHODS Silylation of isomeric cresols was carried out by treatment with N-methyl-N-(trimethylsilyl)trifluoroacetamide. The formed trimethyl(tolyloxy)silanes were analyzed by gas chromatography/mass spectrometry (GC/MS).

  RATIONALE甲酚在许多国家被列为优先控制的污染物，但由于在市场上可买到的色谱柱上色谱分离不完全且质谱几乎相同，因此很难准确测定异构甲酚。方法用N-甲基-N-（三甲基甲硅烷基）三氟乙酰胺处理甲酚的甲硅烷基化反应。通过气相色谱/质谱（GC / MS）分析形成的三甲基（甲苯甲氧基）硅烷。使用密度泛函理论（DFT）方法在B3LYP / 6-311 + G（2d，p）级别上使用高斯03程序进行了理论计算。结果三种异构甲酚和六个异构二甲苯酚的衍生物在HP-5MS毛细管色谱柱上仅用10分钟的气相色谱就已完全分离。此外，由于其在电子电离（EI）-MS中在m / z 91处具有特征性的碱性峰离子，因此可以非常轻松地将邻甲酚与异构体区分开。DFT计算结果表明，m / z 91处大量碎片离子的形成归因于易解离途径，该途径涉及三甲基（邻甲苯基氧基）硅烷的EI-MS中相邻的苯基甲基氢原子的移动。结论甲硅烷基化
• Regioselective and stereoselective cyclizations of cyclohexadienones tethered to active methylene groups
  作者：Rodolfo Tello-Aburto、Kyle A. Kalstabakken、Kelly A. Volp、Andrew M. Harned

  DOI：10.1039/c1ob06125a

  日期：——

  of 2,5-cyclohexadienones tethered to activated methylene groups was studied. The substitution around the cyclohexadienone ring serves to regioselectively direct these cyclizations based primarily on electronic effects. In the case of brominated substrates, these reactions proceed to give highly unusual electron-deficient tricyclic cyclopropanes. By using a Cinchona alkaloid-based phase-transfer catalyst

  研究了拴在活化亚甲基上的2,5-环己二酮的环化作用。主要基于电子效应，环己二烯酮环周围的取代用于区域选择性地引导这些环化反应。在溴化底物的情况下，这些反应会继续产生异常电子缺乏的三环环丙烷。通过使用基于金鸡纳生物碱的相转移催化剂，前手性环己二酮可以中等立体选择性地脱对称。
• Preparation, characterization and use of 3-methyl-1-sulfonic acid imidazolium hydrogen sulfate as an eco-benign, efficient and reusable ionic liquid catalyst for the chemoselective trimethylsilyl protection of hydroxyl groups
  作者：Nader Ghaffari Khaligh

  DOI：10.1016/j.molcata.2011.08.021

  日期：2011.10

  New and novel ionic liquid (3-methyl-1-sulfonic acid imidazolium hydrogen sulfate) is a recyclable and eco-benign catalyst for the chemoselective trimethylsilyl protection of hydroxyl groups under solvent-free conditions to afford trimethylsilanes in excellent yields (92-100%) and in very short reaction times (1-8 min). The catalyst was characterized by FT-IR, H-1 NMR and C-13 NMR studies. All the products were extensively characterized by H-1 NMR, IR, GC-MS and melting point analyses. A mechanism for the catalytic activity is proposed. The catalyst can be recovered and reused without loss of activity. The work-up of the reaction consists of a simple separation, followed by concentration of the crude product and purification. (C) 2011 Elsevier B.V. All rights reserved.
• LAUTERBUCH, MANFRED;JUGER, GUNTER;JANCKE, HARALD;LEHMANN, ANDREAS;ZIMMERM+, CHEM. TECHN. , 42,(1990) N, C. 264-268
  作者：LAUTERBUCH, MANFRED、JUGER, GUNTER、JANCKE, HARALD、LEHMANN, ANDREAS、ZIMMERM+

  DOI：——

  日期：——