4-(三甲基甲硅烷基)苯酚乙酸酯 | 18001-11-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚酯
• 中文名称: 4-(三甲基甲硅烷基)苯酚乙酸酯
• 英文名称: 4-(trimethylsilyl)phenol acetate
• 英文别名: p-(Trimethylsilyl)phenyl Acetate；4-trimethylsilylphenyl acetate；acetic acid-(4-trimethylsilanyl-phenyl ester)；Essigsaeure-(4-trimethylsilyl-phenylester)；(4-Acetoxy-phenyl)-trimethyl-silan；(4-Trimethylsilylphenyl) acetate
• CAS: 18001-11-1
• 化学式: C₁₁H₁₆O₂Si
• 分子量: 208.332
• InChiKey: VLCLGENSXZSWAT-UHFFFAOYSA-N

物化性质

• 沸点：
  135-137 °C(Press: 23 Torr)
• 密度：
  0.98±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.16
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 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-(三甲基甲硅烷基)苯酚乙酸酯 在 N-氯代丁二酰亚胺 、 sodium bromide 作用下， 以 溶剂黄146 为溶剂， 反应 0.17h， 以92%的产率得到4-溴苯基乙酸酯
  参考文献：
  名称：

  Regiospecific incorporation of bromine and iodine into phenols using (trimethylsilyl)phenol derivatives

  摘要：

  DOI：

  10.1021/jo00157a035
• 作为产物：
  描述：

  1-溴-4-(三甲基硅基)苯 在 正丁基锂 、 palladium diacetate 、 [双(三氟乙酰氧基)碘]苯 作用下， 以 四氢呋喃 、 正己烷 、 甲苯 为溶剂， 反应 3.0h， 生成 4-(三甲基甲硅烷基)苯酚乙酸酯
  参考文献：
  名称：

  有机锗烷的正交 C-O 键结构

  摘要：

  我们报告了一种完全正交的 C-O 键形成策略，该策略涉及芳基锗烷与烷基醇（伯醇、仲醇和叔醇）以及羧酸的选择性偶联，耐受其他广泛使用的偶联处理，例如芳香族（伪）卤素（ C–I、C–Br、C–Cl、C–F、C–OTf、C–OFs)、硅烷和硼酸衍生物。这种前所未有的基于 [Ge] 的 C-O 键结构快速（15 分钟到几个小时的反应时间）、耐空气性、操作简单且温和，因为它是无碱的并且在室温下进行。

  DOI：

  10.1021/jacs.3c01081

文献信息

• Gold-Catalyzed Oxidative Coupling Reactions with Aryltrimethylsilanes
  作者：William E. Brenzovich、Jean-François Brazeau、F. Dean Toste

  DOI：10.1021/ol102194c

  日期：2010.11.5

  During continuing studies with a novel oxidative gold oxyarylation reaction, arylsilanes were found to be competent coupling partners, providing further evidence for an intramolecular electrophilic aromatic substitution mechanism. While providing yields complementary to those of the previously described boronic acid methods, the use of trimethylsilanes reduces the observation of homocoupling byproducts

  在对新型氧化金氧芳基化反应的持续研究中，发现芳基硅烷是有效的偶联伙伴，为分子内亲电芳香取代机制提供了进一步的证据。在提供与先前描述的硼酸方法的产率互补的产率的同时，三甲基硅烷的使用减少了对均偶联副产物的观察，并允许进行轻松的分子内偶联反应。
• Silylarene Hydrogenation: A Strategic Approach that Enables Direct Access to Versatile Silylated Saturated Carbo‐ and Heterocycles
  作者：Mario P. Wiesenfeldt、Tobias Knecht、Christoph Schlepphorst、Frank Glorius

  DOI：10.1002/anie.201804124

  日期：2018.7.2

  by arene hydrogenation. The scope includes alkoxy‐ and halosilyl substituents. Silyl groups can be derivatized into a plethora of functionalities and find application in organic synthesis, materials science, and pharmaceutical, agrochemical, and fragrance research. However, silylated saturated (hetero‐ ) cycles are difficult to access with current technologies. The yield of the hydrogenation depends

  我们报告了一种通过芳烃加氢将易得的甲硅烷基化芳烃转化为甲硅烷基化饱和碳和杂环的方法。范围包括烷氧基和卤代甲硅烷基取代基。甲硅烷基可被衍生为多种功能，并在有机合成，材料科学以及制药，农业化学和香料研究中得到应用。但是，目前的技术很难获得甲硅烷基化的饱和（杂）循环。氢化的产率取决于硅胶添加剂的量。这种二氧化硅效应还可以显着改善以前公开的高度氟化芳烃的氢化方法（例如，氢化至全顺式C 6 H 6 F 6）。
• Electrophilic radiofluorination of aryltrimethylsilanes as a general route to 18F-labeled aryl fluorides
  作者：M. Speranza、C.-Y. Shiue、A.P. Wolf、D.S. Wilbur、G. Angelini

  DOI：10.1016/s0022-1139(00)80525-4

  日期：1985.10

  The reactions of a variety of aryltrimethylsilanes with elemental fluorine and acetyl hypofluorite have been studied with the aim of developing a general method for labeling aromatic compounds with fluorine-18. Extensive 18F incorporation into the aromatic ring of the selected aryltrimethylsilanes was invariably observed, leading to the ipso (18F-for-Si) electrophilic substitution products together

  为了开发一种用氟18标记芳族化合物的通用方法，已经研究了各种芳基三甲基硅烷与元素氟和乙酰基次萤石的反应。广泛18 ˚F掺入选定aryltrimethylsilanes的芳香环总是观察到，导致本位（18 F-换Si）的亲电取代产物连同其他（可变产率18 F-用于-H）电取代产物。18的相对范围发现F的取代过程[（（C 1 -Si / C 1 -H）]，主要取决于底物芳环上的取代基，离去部分和所用的放射性氟化方法。讨论了芳基三甲基甲硅烷基衍生物作为快速合成18 F标记的放射性药物的高比活性的前体的用途。
• Rhodium-Catalyzed Silylation and Intramolecular Arylation of Nitriles via the Silicon-Assisted Cleavage of Carbon−Cyano Bonds
  作者：Mamoru Tobisu、Yusuke Kita、Yusuke Ano、Naoto Chatani

  DOI：10.1021/ja804992n

  日期：2008.11.26

  A rhodium-catalyzed silylation reaction of carbon-cyano bonds using disilane has been developed. Under these catalytic conditions, carbon-cyano bonds in aryl, alkenyl, allyl, and benzyl cyanides bearing a variety of functional groups can be silylated. The observation of an enamine side product in the silylation of benzyl cyanides and related stoichiometric studies indicate that the carbon-cyano bond cleavage proceeds through the deinsertion of silyl isocyanide from eta(2)-iminoacyl complex B. Knowledge gained from these studies has led to the development of a new intramolecular biaryl coupling reaction in which aryl cyanides and aryl chlorides are cross-coupled.
• Palladium-Catalyzed Desilylative Acyloxylation of Silicon–Carbon Bonds on (Trimethylsilyl)arenes: Synthesis of Phenol Derivatives from Trimethylsilylarenes
  作者：Keisuke Gondo、Juzo Oyamada、Tsugio Kitamura

  DOI：10.1021/acs.orglett.5b02336

  日期：2015.10.2

  A strategy for desilylative acetoxylation of (trimethylsilyl)-arenes has been developed in which (trimethylsilyl)arenes are converted into acetoxyarenes. The direct acetoxylation is performed in the presence of 5 mol % of Pd(OAc)(2) and PhI(OCOCF3)(2) (1.5 equiv) in AcOH at 80 degrees C for 17 h. The acetoxyarenes are obtained in good to high yields (67-98%). The synthetic utility is demonstrated with a one-pot transformation of (trimethylsilyearenes to phenols by successive acetoxylation and hydrolysis. Furthermore, desilylative acyloxylation of 2-(trimethylsilyl)-naphthalene using several carboxylic acids has been conducted.